Epoxy Resin Composition and Semiconductor Device

ABSTRACT

An epoxy resin composition for encapsulating a semiconductor chip according to this invention comprises (A) a crystalline epoxy resin, (B) a phenol resin represented by general formula (1): 
     
       
         
         
             
             
         
       
     
     wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4 carbon atoms and two or more R1s or two or more R2s are the same or different; a is integer of 0 to 4; b is integer of 0 to 4; c is integer of 0 to 3; and n is average and is number of 0 to 10, (C) a (co)polymer containing butadiene-derived structural unit or its derivative, and (D) an inorganic filler in the amount of 80 wt % to 95 wt % both inclusive in the total epoxy resin composition.

This application is a continuation of U.S. patent application Ser. No.11/289,265, which is based on Japanese patent application Nos.2004-347743, 2004-368714, 2005-002381, 2005-039050 and 2005-099390, thecontents of which are incorporated hereinto by reference.

BACKGROUND

1. Technical Field

This invention relates to an epoxy resin composition for encapsulating asemiconductor chip and a semiconductor device. In particular, thisinvention is suitably used in an area mounting type semiconductor devicewhere a semiconductor chip is mounted on one side of a printed-wiringboard or metal lead frame and substantially only the mounted side isencapsulated with a resin.

2. Related Art

Recent market trend to size reduction, weight saving and higherperformance in electronic devices has led to more integratedsemiconductors. As surface mounting of a semiconductor device has beenaccelerated, there has been newly developed an area mounting typesemiconductor device, with which a semiconductor device with aconventional structure has been replaced.

Such size reduction and thinning in a semiconductor device has demandedmuch lower viscosity and much more strength in an epoxy resincomposition for encapsulating a semiconductor chip. In addition, becauseof environmental concerns, an epoxy resin composition for encapsulatinga semiconductor chip has been increasingly required to be moreflame-resistant without a flame retardant such as bromine-containingcompounds and antimony oxide. Due to the background, a recent epoxyresin composition tends to contain a resin with lower viscosity andlarger amount of an inorganic filler.

As new trend, a lead-free solder with higher melting point than thatconventionally used has been increasingly used for mounting asemiconductor device. When applying the solder, the mounting temperaturemust be higher than that in a conventional process by about 20° C.,sometimes leading to significantly lower reliability of a semiconductordevice after mounting in comparison with a common device. In the lightof such situation, it has been increasingly required to improvereliability of a semiconductor device by improving properties of anepoxy resin composition. For meeting the requirement, there have beeninvestigations of reducing resin viscosity and filling larger amount ofan inorganic filler.

Typical examples of an area mounting type semiconductor device includeBGA (ball grid array) and CSP (chip scale package) with a furthercompacted size, and further packages such as QFN and SON with thesmaller mounting area than conventional QFP or SOP. These packages suchas QFN and SON were developed to solve the demands of high pin count andhigh-speed. These demands approach the limit in an area mounting typesemiconductor device represented by conventional QFP, SOP and so on.

BGA and CSP are encapsulated by molding an epoxy resin composition ononly the side, where the semiconductor chip is mounting, of a hardcircuit board such as a circuit board consists of BT resin/copper foil(a bismaleimide-triazine resin/glass fabric substrate) is represented,of a flexible printed circuit board such as a circuit board consists ofa polyimide resin film/copper foil is represented. Furthermore, onopposite side of side of a substrate on which a semiconductor chip ismounted, the solder ball is formed in parallel in two dimensions to bemounted on circuit board by soldering.

As described above, the structure of BGA or CSP is a one-sideencapsulated structure where only a side of a substrate on which asemiconductor chip is mounted is encapsulated with an epoxy resincomposition (and a side of a substrate on which a solder ball is formedis not encapsulated). Therefore, such a semiconductor device tends to bewarped immediately after molding, due to unconformity in thermalexpansion and thermal shrinkage between the organic substrate or themetal substrate and the cured epoxy-resin composition, or curingshrinkage of the epoxy resin composition during molding curing.

Furthermore, warpage in a semiconductor device causes a joining point ofsolder balls to be not located horizontally. Therefore, a semiconductordevice is lifted from a circuit board during packaging thesesemiconductor devices by the solder joint on a circuit board, leading todeterioration in reliability of electric connection.

On the contrary, QFN or SON has been produced with the same design asconventional QFP or SOP. There have been recently, however, producedpackages by mounting the matrix of semiconductor chips on one side of ametal substrate (for example, a laminate of a copper-lead frame,nickel-palladium+gold-plated lead frame stacked with a polyimide film),encapsulating them with an epoxy resin composition for encapsulating inone batch and cutting the substrate into lattice with a given size togive individual packages (hereinafter, referred to as MAP-QFN andMAP-SON) (for example, see Japanese Patent Laid-open No. 2003-109983).

As in the case of BGA or CSP, the structure of MAP-QFN or MAP-SON is aone-side encapsulated structure where only a side of a substrate onwhich a semiconductor chip is mounted is encapsulated with an epoxyresin composition. Here, an encapsulated area of MAP-QFN or MAP-SON islarger than common package molding and only one side is encapsulated.Therefore, such a semiconductor device tends to be warped immediatelyafter molding, due to unconformity in thermal expansion and thermalshrinkage between the metal substrate and the cured epoxy-resincomposition or curing shrinkage of the epoxy resin composition duringmolding curing.

Warpage in a semiconductor device causes a semiconductor device to belifted from a circuit board for mounting that, leading to deteriorationin reliability of electric connection.

For reducing warpage in an area mounting type semiconductor device inwhich substantially one side of an organic substrate or a metalsubstrate is encapsulated with an epoxy resin composition, it isimportant to approximate a thermal expansion coefficient of a substratewith that of a cured epoxy resin composition and to reduce curingshrinkage in an epoxy resin composition during molding curing.

To achieve them, there has been already suggested the technique that amultifunctional epoxy resin and a multifunctional phenol resin arecombined to increase Tg of an epoxy resin composition and the content ofan inorganic filler is adjusted to match α1. Combination of amultifunctional epoxy resin with a multifunctional phenol resin may,however, reduce fluidity to cause problems such as unfilled voids.

When soldering is conducted by solder processing such as infraredreflow, vapor phase soldering and solder immersion, moisture presentwithin a semiconductor device due to moisture absorption by a curedepoxy resin composition (molding) is rapidly vaporized at elevatedtemperature. A stress generated during the process may cause cracks inthe semiconductor device or peeling in an interface between the surfacemounting the semiconductor chip in the metal substrate and the curedepoxy resin composition. Therefore, it is needed to reduce a warpage ina semiconductor device by increasing the content of an inorganic filler.It is needed to reduce a stress by reducing hygroscopicity of a molding.Furthermore, improvement in heat resistance of a molding and improvedadhesiveness between a cured material and a metal substrate are alsoneeded.

There has been developed the technique for maintaining high fluidity ofan epoxy resin composition used in a surface-mounted semiconductordevice such as conventional QFP and SOP during molding. For example,there have been disclosed using a resin with low melt viscosity (forexample, see Japanese Patent Laid-open No. 1995-130919) and surfacetreatment of an inorganic filler with a silane coupling agent forincreasing the content of an inorganic filler (for example, see JapanesePatent Laid-open No. 1996-20673). Any of these techniques can meet onlyone of various required properties.

As described above, it is necessary to add an inorganic filler at highconcentration for cured material property improvement such as reducedwarpage and reduced stress in a molding formed from an epoxy resincomposition for encapsulating a semiconductor chip. Furthermore, forimproving filling properties of an epoxy resin composition forencapsulating a semiconductor chip, its fluidity must be improved.However, when filling an inorganic filler at high concentration,fluidity of an epoxy resin composition for encapsulating a semiconductorchip is reduced. Thus, there is trade-off relationship between fluidityof an epoxy resin composition for encapsulating a semiconductor chip andcured material properties of a molding.

There have been still needs for an epoxy resin composition forencapsulating a semiconductor chip excellent in both fluidity and curedmaterial properties in a molding, as well as a semiconductor deviceproduced using the composition.

SUMMARY OF THE INVENTION

An objective of this invention for solving the problems in the prior artis to provide an epoxy resin composition for encapsulating asemiconductor chip excellent in both fluidity and cured materialproperties in a molding, as well as a semiconductor device producedusing the composition.

According to present invention, there are provided the followings.

[1]

An epoxy resin composition for encapsulating a semiconductor chipcomprising

(A) a crystalline epoxy resin,

(B) a phenol resin represented by general formula (1):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10,

(C) a (co)polymer containing butadiene-derived structural unit or itsderivative, and

(D) an inorganic filler in the amount of 80 wt % to 95 wt % bothinclusive in the total epoxy resin composition.

[2]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [1],

wherein said phenol resin (B) is represented by general formula (2):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10;

said (co)polymer or its derivative (C) is an epoxidized polybutadienecompound (C-1); and

said inorganic filler (D) is contained in the amount of 85 wt % to 95 wt% both inclusive in the total epoxy resin composition.

[3]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [2],

wherein the number average molecular weight of said epoxidizedpolybutadiene compound (C-1) is 500 to 4000 both inclusive.

[4]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [2], further comprising a curing accelerator (E).

[5]

A semiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asdescribed in any of [2] to [4].

[6]

An area mounting type epoxy resin composition for encapsulating asemiconductor chip which is the epoxy resin composition forencapsulating a semiconductor chip as described in any of [2] to [4]used for encapsulating an area mounting type semiconductor device,

wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.

[7]

An area mounting type semiconductor device, wherein a semiconductor chipis encapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as described in [6].

[8]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [1],

wherein said phenol resin (B) is represented by general formula (2):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10,

wherein said (co)polymer or its derivative (C) is abutadiene-acrylonitrile copolymer (C-2).

[9]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [8]

wherein said butadiene-acrylonitrile copolymer (C-2) is acarboxyl-terminated butadiene-acrylonitrile copolymer represented bygeneral formula (3):

wherein Bu represents a butadiene-derived structural unit; ACNrepresents an acrylonitrile-derived structural unit; x is positivenumber of less than 1; y is positive number of less than 1; x+y=1; and zis integer of 50 to 80.

[10]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [8],

wherein said butadiene-acrylonitrile copolymer (C-2) is contained in theamount of 0.05 wt % to 0.5 wt % both inclusive in the total epoxy resincomposition.

[11]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [8]

wherein said inorganic filler (D) is contained in the amount of 85 wt %to 95 wt % both inclusive in the total epoxy resin composition.

[12]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [8], further comprising a curing accelerator (E).

[13]

A semiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asdescribed in any of [8] to [12].

[14]

An area mounting type epoxy resin composition for encapsulating asemiconductor chip which is the epoxy resin composition forencapsulating a semiconductor chip as described in any of [8] to [12]used for encapsulating an area mounting type semiconductor device,

wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.

[15]

An area mounting type semiconductor device, wherein a semiconductor chipis encapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as described in [14].

[16]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [1],

wherein said crystalline epoxy resin (A) is represented by generalformula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different,

said phenol resin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5,

said (co)polymer or its derivative (C) is a polybutadiene having theintramolecular oxirane structure (C-3) with the oxirane-oxygen contentof 3% to 10% both inclusive, and

said inorganic filler (D) is contained in the amount of 85 wt % to 95 wt% both inclusive in the total epoxy resin composition; and

further comprising (F) an epoxy resin represented by general formula(6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

[17]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [16],

wherein said polybutadiene having the intramolecular oxirane structure(C-3) has a viscosity of 20 Pa·s to 700 Pa·s both inclusive at 25° C.

[18]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [16], further comprising a curing accelerator (E).

[19]

A semiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asdescribed in any of [16] to [18].

[20]

An area mounting type epoxy resin composition for encapsulating asemiconductor chip which is the epoxy resin composition forencapsulating a semiconductor chip as described in any of [16] to [18]used for encapsulating an area mounting type semiconductor device,

wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.

[21]

An area mounting type semiconductor device, wherein a semiconductor chipis encapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as described in [20].

[22]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [1],

wherein said crystalline epoxy resin (A) is represented by generalformula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different,

said phenol resin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5, and

said (co)polymer or its derivative (C) is an epoxidized polybutadienecompound (C-1),

said inorganic filler (D) is contained in the amount of 80 wt % to 94 wt% both inclusive in the total epoxy resin composition;

further comprising (F) an epoxy resin represented by general formula(6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5; and

wherein the weight ratio [(F)/(A)] of said epoxy resin (F) to saidcrystalline epoxy resin (A) represented by general formula (4) is 10/90to 90/10 both inclusive.

[23]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [22],

wherein said epoxidized polybutadiene compound (C-1) has the numberaverage molecular weight of 500 to 4000 both inclusive.

[24]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [22], further comprising a curing accelerator (E).

[25]

A semiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asdescribed in any of [22] to [24].

[26]

An area mounting type epoxy resin composition for encapsulating asemiconductor chip which is the epoxy resin composition forencapsulating a semiconductor chip as described in any of [22] to [24]used for encapsulating an area mounting type semiconductor device,

wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.

[27]

An area mounting type semiconductor device, wherein a semiconductor chipis encapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as described in [26]

[28]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [1],

wherein said crystalline epoxy resin (A) is represented by generalformula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different,

said phenol resin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5, and

said (co)polymer or its derivative (C) is a butadiene-acrylonitrilecopolymer (C-2); and

further comprising (F) an epoxy resin represented by general formula(6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

[29]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [28]

wherein said butadiene-acrylonitrile copolymer (C-2) is acarboxyl-terminated butadiene-acrylonitrile copolymer represented bygeneral formula (3):

wherein Bu represents a butadiene-derived structural unit; ACNrepresents an acrylonitrile-derived structural unit; x is positivenumber of less than 1; y is positive number of less than 1; x+y=1; and zis integer of 50 to 80.

[30]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [28],

wherein said butadiene-acrylonitrile copolymer (C-2) is contained in theamount of 0.05 wt % to 0.5 wt % both inclusive in the total epoxy resincomposition.

[31]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [28],

wherein the weight ratio [(F)/(A)] of the epoxy resin (F) to thecrystalline epoxy resin (A) represented by general formula (4) is 10/90to 90/10 both inclusive.

[32]

The epoxy resin composition for encapsulating a semiconductor chip asdescribed in [28], further comprising a curing accelerator (E).

[33]

A semiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asdescribed in any of [28] to [32].

[34]

An area mounting type epoxy resin composition for encapsulating asemiconductor chip which is the epoxy resin composition forencapsulating a semiconductor chip as described in any of [28] to [32]used for encapsulating an area mounting type semiconductor device,

wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.

[35]

An area mounting type semiconductor device, wherein a semiconductor chipis encapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as described in [34].

An epoxy resin composition for encapsulating a semiconductor chipaccording to the present invention can allow for higher filling rate ofan inorganic filler and higher fluidity in comparison with the priorart. The epoxy resin composition for encapsulating a semiconductor chipaccording to the present invention can, therefore, exhibit good curedmaterial properties such as warpage reduction in a molding and a reducedstress and good filling properties. Thus, it is particularly suitablefor an area mounting type epoxy resin composition for encapsulating asemiconductor chip and a semiconductor device with the composition.

DETAILED DESCRIPTION

The invention will be now described herein with reference toillustrative embodiments. Those skilled in the art will recognize thatmany alternative embodiments can be accomplished using the teachings ofthe present invention and that the invention is not limited to theembodiments illustrated for explanatory purpose.

An epoxy resin composition for encapsulating a semiconductor chipaccording to the present invention contains the following components (A)to (D):

(A) a crystalline epoxy resin,

(B) a phenol resin represented by general formula (1):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10,

(C) a (co)polymer containing butadiene-derived structural unit or itsderivative, and

(D) an inorganic filler.

The inorganic filler (D) is contained in the amount of 80 wt % to 95 wt% both inclusive in the total epoxy resin composition.

An epoxy resin composition for encapsulating a semiconductor chip havingsuch a composition can satisfy both requirements of reduction in thermalexpansion by higher content of the inorganic filler (D) and reduction inelasticity by adding the (co)polymer having a butadiene-derivedstructural unit or its derivative (C) Thus, the epoxy resin compositionfor encapsulating a semiconductor chip exhibits improved fluidity,reduced warpage in a cured material and soldering resistance, which arerequired to an area mounting type semiconductor device. There can be,therefore, more reliable semiconductor device.

There will be detailed an epoxy resin composition for encapsulating asemiconductor chip according to the present invention.

Crystalline Epoxy Resin (A)

Examples of a crystalline epoxy resin (A) used in this invention includeglycidyl ether of hydroquinone, bisphenol-F type epoxy resins, biphenyltype epoxy resins represented by general formula (7), stilbene typeepoxy resins represented by general formula (8) and epoxy resinsrepresented by general formula (4).

wherein R3 to R10 are hydrogen or alkyl having up to 4 carbon atoms andare the same or different.

wherein R11 to R20 are hydrogen or alkyl having up to 4 carbon atoms andare the same or different.

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms and two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms and two or more R2s are the same or different.

Phenol Resin (B)

A phenol resin (B) used in this invention is represented by generalformula (1):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms, and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; n is average and is number of 0 to 10.

(Co)Polymer Having a Butadiene-Derived Structural Unit or its Derivative(C)

A (co)polymer having a butadiene-derived structural unit or itsderivative (C) used in this invention (hereinafter, sometimes simplyreferred to as “(co)polymer or its derivative (C)”) is a (co)polymer orits derivative (C), which is prepared from butadiene as a monomer.

The (co)polymer or its derivative (C) may be an epoxidized polybutadienecompound (C-1), a butadiene-acrylonitrile copolymer (C-2) or apolybutadiene having an oxirane structure (C-3). These compounds will bedescribed later.

Inorganic Filler (D)

An inorganic filler (D) used in this invention may be selected fromthose generally used for an epoxy resin composition for encapsulating asemiconductor chip.

These may include fused silica, crystalline silica, secondary aggregatedsilica, alumina, titanium white, aluminum hydroxide, talc, clay andglass fiber, which may be used alone or in combination of two or more.Fused silica is particularly preferable. Fused silica may be in the formof milled particles or spheres. More preferably, spherical silica may beused for increasing its content and minimizing increase in meltviscosity of an epoxy resin composition. In order to increase thecontent of spherical silica, it is desirable to adjust size distributionof the spherical silica to be relatively wider.

Furthermore, an inorganic filler may be, if necessary, surface-treatedwith a coupling agent, an epoxy resin or a phenol resin. Surfacetreatment may be conducted by appropriate process such as removing asolvent after blending them in the solvent and directly adding theadditives to an inorganic filler to give a mixture which is then treatedusing a mixer.

An epoxy resin composition for encapsulating a semiconductor chipaccording to this invention may contain, in addition to components (A)to (D) described above, a curing accelerator (E), an epoxy resin (F) anda silane coupling agent (G).

Curing Accelerator (E)

A curing accelerator (E) may be selected from, without any particularrestrictions, those capable of accelerating reaction of an epoxy groupwith a phenolic hydroxyl group, including

diazabicycloalkenes and their derivatives such as1,8-diazabicyclo(5,4,0)undecene-7;

organophosphines and their derivatives such as triphenylphosphine andmethyldiphenylphosphine; and

tetra-substituted phosphonium.tetra-substituted borates such astetraphenylphosphonium.tetraphenylborate,tetraphenylphosphonium.tetrabenzoic acid borate,tetraphenylphosphonium.tetranaphthoic acid borate,tetraphenylphosphonium/tetranaphthoyloxyborate, andtetraphenylphosphonium.tetranaphthyloxyborate. These may be used aloneor in combination of two or more.

Epoxy Resin (F)

An epoxy resin (F) may be an epoxy resin represented by general formula(6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

Silane Coupling Agent (G)

A silane coupling agent (G) may be a compound represented by generalformula (9):

R3-NH—R4-Si(OR5)_(n)R6_(3-n)  (9)

wherein R3 is an organic group having 1 to 12 carbon atoms; R4, R5 andR6 are hydrocarbon having 1 to 12 carbon atoms; R3 to R6 are the same ordifferent; and n is integer of 1 to 3.

Other Components

In necessary, an epoxy resin composition of this invention mayappropriately contain, in addition to components (A) to (G) describedabove, any of various additives, including

-   -   a natural wax such as carnauba wax;

a synthetic wax such as polyethylene wax;

a higher fatty acid or its metal salts such as stearic acid and zincstearate;

a mold release such as paraffin;

a coloring agent such as carbon black and red ocher;

a flame retardant such as brominated epoxy resins, antimony trioxide,aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdenumoxide, phosphazene and phosphorous compounds;

an inorganic ion exchanger such as bismuth oxide hydrate; and

a low stress component such as silicone oils and rubbers; and

an antioxidant.

An epoxy resin composition of this invention may be prepared by mixingcomponents (A) to (G) and other additives at ambient temperature using,for example, a mixer, kneading the mixture with heating by kneadingmeans such as a roller mill, a kneader and an extruder, and cooling andthen milling the mixture.

For manufacturing a semiconductor device by encapsulating an electronicpart such as a semiconductor chip using an epoxy resin composition ofthis invention, curing molding may be conducted by a conventionalmolding process such as transfer molding, compression molding andinjection molding. Other methods involved in manufacturing asemiconductor device may be selected from well-known methods. Inparticular, an epoxy resin composition of this invention is mostsuitable for an area mounting type semiconductor device.

Preferred embodiments of this invention will be described.

EMBODIMENT 1

An epoxy resin composition for encapsulating a semiconductor chip ofEmbodiment 1 contains the following components (A) to (E):

(A) a crystalline epoxy resin,

(B) a phenol resin represented by general formula (2),

(C-1) an epoxidized polybutadiene compound,

(D) an inorganic filler in the amount of 85 wt % to 95 wt % bothinclusive in the total epoxy resin composition, and

(E) a curing accelerator.

The epoxidized polybutadiene compound (C-1) is contained in the amountof 0.05 wt % to 5 wt % both inclusive in the total epoxy resincomposition.

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10.

Such an epoxy resin composition for encapsulating a semiconductor chipcan meet both reduction in thermal expansion by higher content of theinorganic filler (D) and reduction in elasticity by adding theepoxidized polybutadiene compound (C-1). The epoxy resin composition forencapsulating a semiconductor chip is highly fluent and thus hasimproved filling properties. Furthermore, the epoxy resin compositionfor encapsulating a semiconductor chip can provide a molding exhibitingexcellent cured material properties such as reduced warpage andsoldering resistance. The composition can be, therefore, significantlyeffective to give a highly reliable semiconductor device. As describedabove, the epoxy resin composition for encapsulating a semiconductorchip of this embodiment can be suitably used for an area mounting typesemiconductor device.

There will be specifically described Embodiment 1.

Crystalline Epoxy Resin (A)

Examples of a crystalline epoxy resin (A) used in Embodiment 1 includeglycidyl ether of hydroquinone, bisphenol-F type epoxy resins, biphenyltype epoxy resins represented by general formula (7) and stilbene typeepoxy resins represented by general formula (8).

wherein R3 to R10 are hydrogen or alkyl having up to 4 carbon atoms andare the same or different.

wherein R11 to R20 are hydrogen or alkyl having up to 4 carbon atoms andare the same or different.

These epoxy resins is solid at ambient temperature so that it exhibitsgood handling properties, and has low melt viscosity during molding. Alower melt viscosity can improve fluidity of the epoxy resin compositionfor encapsulating a semiconductor chip and allows for filling theinorganic filler at higher concentration. Thus, moisture resistance canbe improved and difference in coefficient of linear expansion can bereduced, resulting in improved properties as a molding.

Preferable examples of the biphenyl type epoxy resin represented bygeneral formula (7) include 4,4′-diglycidylbiphenyl,3,3′,5,5′-tetramethyl-4,4′-diglycidylbiphenyl and a fused mixture ofthese compounds, which are well-balanced in workability andpracticability.

Preferable examples of the stilbene type epoxy resin represented bygeneral formula (8) include5-tert-butyl-4,4′-glycidyl-2,3′,5′-trimethylstilbene,4,4′-diglycidyl-3,3′,5,5′-tetramethylstilbene and a fused mixture ofthese compounds, which are well-balanced in workability andpracticability.

Such a crystalline epoxy resin (A) may be used in combination withanother epoxy resin.

When using them in combination, the content of the crystalline epoxyresin (A) is preferably at least 10 wt %, more preferably 30 wt % ormore, further preferably 50 wt % or more in the total epoxy resin. Thecrystalline epoxy resin (A) can be added within the above range, toimprove fluidity of an epoxy resin composition for encapsulating asemiconductor chip.

Examples of an epoxy resin which can be combined include, but notlimited to, phenol novolac type epoxy resins, cresol novolac type epoxyresins, triphenolmethane type epoxy resins, phenolaralkyl type epoxyresins, naphthol type epoxy resins, naphthalene type epoxy resins,alkyl-modified triphenolmethane type epoxy resins, epoxy resinscontaining triazine-core and dicyclopentadiene-modified phenol typeepoxy resins, which can be used alone or in combination of two or more.It is desirable that an epoxy resin combined has viscosity as low aspossible for avoiding deterioration in the advantageous property of thecrystalline epoxy resin, that is, lower melt viscosity during molding.

Phenol Resin (B)

A phenol resin (B) used in this embodiment may be a phenol resinrepresented by general formula (2).

The phenol resin represented by general formula (2) has a hydrophobicand rigid biphenylene moiety between phenolic hydroxyl groups. Thus, thephenol resin (B) having a biphenylene moiety can be used to reducewarpage in a cured product (molding) of an epoxy resin composition forencapsulating a semiconductor chip. Furthermore, the molding has reducedmoisture-absorption rate, has lower elasticity modulus in hightemperature range over Tg and exhibits good adhesiveness to asemiconductor chip, an organic substrate and a metal substrate. It alsohas features that it is highly flame-resistance and exhibits higher heatresistance in spite of its low crosslinking density.

In the light of curing properties, the phenol resin represented bygeneral formula (2) is preferably a phenol resin represented by generalformula (10).

wherein n is average and is number of 0 to 10.

In general formulas (2) and (10), when n is within the above range,fluidity of a resin composition during molding can be improved,resulting in increase in content of an inorganic filler, which cancontribute to lowering hygroscopicity and reduction in warpage.

The phenol resin represented by general formula (2) used in Embodiment 1can be used in combination with another phenol resin. When using them incombination, the content of the phenol resin (B) represented by generalformula (2) is preferably at least 10 wt %, more preferably 30 wt % ormore, further preferably 50 wt % or more in the total phenol resin. Thephenol resin (B) can be added within the above range to provide an epoxyresin composition exhibiting low elasticity at high temperature and lowhygroscopicity, and further good adhesiveness and flame resistance.

Examples of a phenol resin which can be used in combination include, butnot limited to, phenol novolac resins, cresol novolac resins, naphtholaralkyl resins, triphenolmethane resins, terpene-modified phenol resins,dicyclopentadiene-modified phenol resins and phenol aralkyl resinshaving a phenylene moiety. These can be used alone or in combination oftwo or more. For higher content of the inorganic filler, it ispreferably of low viscosity as with an epoxy resin.

An equivalence ratio of the number of epoxy groups in the total epoxyresin to the number of phenolic hydroxyl groups in the total phenolresin used in Embodiment 1 is preferably 0.5 to 2 both inclusive,particularly preferably 0.7 to 1.5 both inclusive. When the equivalenceratio is within the above range, an epoxy resin composition forencapsulating a semiconductor chip which provides a molding exhibitinggood moisture resistance and curing properties, can be obtained.

Epoxidized Polybutadiene Compound (C-1)

An epoxidized polybutadiene compound (C-1) used in Embodiment 1 may be,but not limited to, a compound represented by general formula (11).

wherein k, l, m and n are integer of 1 to 50; R21 has structurerepresented by C_(p)H_(q); p is integer of 0 to 10; and q is integer of1 to 21.

A content of the epoxidized polybutadiene compound (C-1) is preferably0.05 wt % to 5 wt % both inclusive, particularly preferably 0.1 wt % to2 wt % both inclusive in the total epoxy resin composition. The contentwithin the above range may result in reduction in elasticity modulus andfurther lowering of viscosity of the epoxy resin composition.

In addition, the number average molecular weight of the epoxidizedpolybutadiene compound (C-1) used in this embodiment is preferably 500to 4000 both inclusive. The number average molecular weight within theabove range may result in reduction in elasticity modulus of the epoxyresin composition and desired viscosity.

Inorganic Filler (D)

An inorganic filler (D) used in Embodiment 1 may be the inorganic fillerdescribed above. A content of the inorganic filler used in thisembodiment is 85 wt % to 95 wt % both inclusive, preferably 87 wt % to93 wt % both inclusive in the total epoxy resin composition. When thecontent of the inorganic filler (D) is within the above range, a moldingprepared may have adequately reduced hygroscopicity and thermalexpansion, resulting in good soldering resistance and reduction inwarpage in a semiconductor device. Furthermore, fluidity of an epoxyresin composition for encapsulating a semiconductor chip can beimproved, so that it can be reliably filled during molding and thusproblems such as gold-wire deformation can be prevented.

Curing Accelerator (E)

A curing accelerator (E) used in Embodiment 1 may be the above compound.

Other Components

An epoxy resin composition of this embodiment may contain the othercomponents described above in addition to components (A), (B), (C-1),(D) and (E). Furthermore, the composition may appropriately contain, ifnecessary, any of various additives including a silane coupling agentsuch as epoxysilanes, mercaptosilanes, aminosilanes, alkylsilanes,ureidosilanes and vinylsilanes and coupling agents such as titanatecoupling agents, aluminum coupling agents and aluminum/zirconiumcoupling agents.

An epoxy resin composition of Embodiment 1 may be prepared by mixingcomponents (A) to (E) and other additives at ambient temperature using,for example, a mixer, kneading the mixture with heating by kneadingmeans such as a roller mill, a kneader and an extruder, and cooling andthen milling the mixture.

For manufacturing a semiconductor device by encapsulating an electronicpart such as a semiconductor chip using an epoxy resin composition ofEmbodiment 1, curing molding may be conducted by a conventional moldingprocess such as transfer molding, compression molding and injectionmolding. Other methods involved in manufacturing a semiconductor devicemay be selected from well-known methods. In particular, an epoxy resincomposition of this embodiment is most suitable for an area mountingtype semiconductor device.

EMBODIMENT 2

An epoxy resin composition for encapsulating a semiconductor chip ofEmbodiment 2 contains the following components (A) to (C-2):

(A) a crystalline epoxy resin,

(B) a phenol resin represented by general formula (2),

(C-2) a butadiene-acrylonitrile copolymer.

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10.

Such an epoxy resin composition may meet both higher content of aninorganic filler and higher fluidity. Furthermore, the epoxy resincomposition for encapsulating a semiconductor chip can provide a moldingexhibiting excellent cured material properties such as reduced warpageand soldering resistance. The composition can be, therefore,significantly effective to give a highly reliable semiconductor device.As described above, the epoxy resin composition for encapsulating asemiconductor chip of this embodiment can be suitably used for an areamounting type semiconductor device.

There will be specifically described Embodiment 2.

Crystalline Epoxy Resin (A)

A crystalline epoxy resin (A) used in Embodiment 2 can be as describedin Embodiment 1

The crystalline epoxy resin (A) of this embodiment may be combined withanother epoxy resin as described in Embodiment 1. When using them incombination, the content of the crystalline epoxy resin (A) ispreferably at least 10 wt %, more preferably 30 wt % or more, furtherpreferably 50 wt % or more in the total epoxy resin. The crystallineepoxy resin (A) can be added within the above range, to improve fluidityof epoxy resin composition.

Phenol Resin (B)

A phenol resin (B) used in Embodiment 2 may be a compound represented bygeneral formula (2) as described in Embodiment 1.

The phenol resin (B) in Embodiment 2 may be combined with another phenolresin as described in Embodiment 1. When using them in combination, thecontent of the phenol resin (B) is preferably at least 10 wt %, morepreferably 30 wt % or more, further preferably 50 wt % or more in thetotal phenol resin. The phenol resin (B) within the above range can beadded to an epoxy resin composition for encapsulating a semiconductorchip to provide a molding exhibiting low elasticity at high temperatureand low hygroscopicity, and further good adhesiveness and flameresistance.

An equivalence ratio of the number of epoxy groups in the total epoxyresin to the number of phenolic hydroxyl groups in the total phenolresin used in this embodiment is preferably 0.5 to 2 both inclusive,particularly preferably 0.7 to 1.5 both inclusive. When the equivalenceratio is within the above range, an epoxy resin composition exhibitinggood moisture resistance and curing properties can be obtained.

Butadiene-Acrylonitrile Copolymer (C-2)

A butadiene-acrylonitrile copolymer (C-2) used in Embodiment 2 may be,but not limited to, a compound represented by general formula (3), bothof whose ends have a carboxyl group.

wherein Bu represents a butadiene-derived structural unit; ACNrepresents an acrylonitrile-derived structural unit; x is positivenumber of less than 1; y is positive number of less than 1; x+y=1; and zis integer of 50 to 80.

The carboxyl groups in the butadiene-acrylonitrile copolymer (C-2) cancombine an inorganic filler and an epoxy resin as starting materials foran epoxy resin composition for encapsulating, with a semiconductor chipand an organic substrate as semiconductor device members.

A content of the butadiene-acrylonitrile copolymer (C-2) used in thisembodiment is preferably 0.05 to 0.5 wt % both inclusive, morepreferably 0.1 wt % to 0.3 wt % both inclusive in the total epoxy resincomposition.

The content within the above range can improve soldering resistancebecause it brings about good adhesiveness between a cured product froman epoxy resin composition for encapsulating a semiconductor chip and asubstrate. Furthermore, the epoxy resin composition can becomeadequately fluent to be reliably filled during molding, resulting inprevention of gold-wire deformation within a semiconductor device.

An epoxy resin composition for encapsulating a semiconductor chip ofthis embodiment may contain, in addition to components (A) to (C-2)described above, an inorganic filler (D) and/or a curing accelerator(E).

Inorganic Filler (D)

An inorganic filler (D) used in Embodiment 2 may be the filler asdescribed in Embodiment 1. A content of the inorganic filler (D) used inthis embodiment is 85 wt % to 95 wt % both inclusive, preferably 87 to93 wt % both inclusive in the total epoxy resin composition. When thecontent of the inorganic filler (D) is within the above range, a moldingprepared may have adequately reduced hygroscopicity and thermalexpansion, resulting in good soldering resistance and reduction inwarpage in a semiconductor device. Furthermore, fluidity of an epoxyresin composition for encapsulating a semiconductor chip can beimproved, so that it can be reliably filled during molding and thusproblems such as gold-wire deformation can be prevented.

Curing Accelerator (E)

A curing accelerator (E) used in Embodiment 2 may be the compound asdescribed in Embodiment 1.

Other Components

An epoxy resin composition in Embodiment 2 may be selected from those asdescribed in Embodiment 1 or others.

The epoxy resin composition in Embodiment 2 can be prepared as describedin Embodiment 1. Furthermore, the epoxy resin composition can be used toencapsulate an electronic part such as a semiconductor chip to prepare asemiconductor device as described in Embodiment 1.

EMBODIMENT 3

An epoxy resin composition for encapsulating a semiconductor chipaccording to Embodiment 3 contains the following components (A) to (G).

(A) a crystalline epoxy resin represented by general formula (4),

(B) a phenol resin represented by general formula (5),

(C-3) a polybutadiene having the intramolecular oxirane structure,

(D) a curing accelerator,

(E) an inorganic filler in the amount of 85 wt % to 95 wt % bothinclusive in the total epoxy resin composition,

(F) an epoxy resin represented by general formula (6), and

(G) a silane coupling agent represented by general formula (9).

An oxirane-oxygen content in the polybutadiene (C-3) is 3% to 10% bothinclusive.

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms and two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms and two or more R2s are the same or different.

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms, and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms, and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

R3-NH—R4-Si(OR5)_(n)R6_(3-n)  (9)

wherein R3 is an organic group having 1 to 12 carbon atoms; R4, R5 andR6 are hydrocarbon having 1 to 12 carbon atoms; R3 to R6 are the same ordifferent; and n is integer of 1 to 3.

Such an epoxy resin composition may meet both higher content of aninorganic filler and higher fluidity. Furthermore, the epoxy resincomposition for encapsulating a semiconductor chip can provide a moldingexhibiting excellent cured material properties such as reduced warpageand soldering resistance. The composition can be, therefore,significantly effective to give a highly reliable semiconductor device.As described above, the epoxy resin composition for encapsulating asemiconductor chip of this embodiment can be suitably used for an areamounting type semiconductor device.

There will be specifically described Embodiment 3.

Crystalline Epoxy Resin (A)

A crystalline epoxy resin (A) used in Embodiment 3 may be a crystallineepoxy resin represented by general formula (4). The crystalline epoxyresin (A) represented by general formula (4) is a solid at ambienttemperature, but becomes extremely low viscous liquid at temperatureover its melting point, so that an inorganic filler can be added inhigher content. An epoxy resin composition containing the resin can,therefore, exhibit excellent soldering resistance.

The crystalline epoxy resin (A) represented by general formula (4) maybe, for example, a bisphenol A type epoxy resin, but there are noparticular restrictions as long as it has the structure of generalformula (4).

A content of another epoxy resin combined is, if any, preferably suchthat the epoxy resin (F) and the crystalline epoxy resin (A) amount to70 wt % to 100 wt % both inclusive to the total epoxy resin. When thetotal amount of the epoxy resin (F) and the crystalline epoxy resin (A)is within the above range, a cured product can has lower moistureabsorption rate and exhibit excellent crack resistance.

An epoxy resin which can be combined may be a monomer, oligomer orpolymer having an intramolecular epoxy group. Examples of an epoxy resinwhich can be combined include phenol novolac type epoxy resins,ortho-cresol novolac type epoxy resins, naphthol novolac type epoxyresins, phenol aralkyl type epoxy resins having a phenylene moiety,naphthol aralkyl type epoxy resins (having, for example, a phenylene orbiphenyl moiety), dicyclopentadiene-modified phenol type epoxy resins,stilbene type epoxy resins, triphenolmethane type epoxy resins,alkyl-modified triphenolmethane type epoxy resins and epoxy resinscontaining triazine-core. The epoxy resin, which can be combined, may beone or combination of two or more selected from these compounds.

Phenol Resin (B)

A phenol resin (B) used in Embodiment 3 may be a phenol resinrepresented by general formula (5).

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms, and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5.

The phenol resin represented by general formula (5). has a hydrophobicand rigid biphenylene moiety between phenolic hydroxyl groups. A curedproduct prepared from an epoxy resin composition containing the phenolresin has reduced moisture-absorption rate and lower elasticity modulusin high temperature range over Tg. It also exhibits good adhesiveness toa semiconductor chip, an organic substrate and a metal substrate. Italso has the feature that it exhibits higher heat resistance in spite ofits low crosslinking density. Therefore, a semiconductor deviceencapsulated with a resin composition containing the phenol resinexhibits excellent crack resistance.

In general formula (5), n is average and is positive number of 1 to 5,preferably integer of 1 to 3. With n within the above range, an epoxyresin composition exhibits good curing properties and improved fluidity.The phenol resins represented by general formula (5) may be used aloneor in combination of two or more.

The phenol resin represented by general formula (5) may be, for example,a phenol biphenyl aralkyl resin, but there are no particularrestrictions as long as it has the structure of general formula (5).

In this embodiment, another phenol resin may be combined as long as itdoes not deteriorate the features obtained by using the phenol resin (B)represented by general formula (5). A content of the additional phenolresin combined is preferably such that the content of the phenol resin(B) is 70 wt % to 100 wt % both inclusive in the total phenol resin.With the content of the phenol resin (B) within the above range, a curedproduct has a reduced moisture-absorption rate. Furthermore, the curedproduct exhibits excellent adhesiveness to a base material and solderingresistance after soldering.

The additional phenol resin may be a monomer, oligomer or polymer havingan intramolecular phenolic hydroxyl group, which desirably has viscosityas low as possible. Examples include phenol novolac resins, cresolnovolac resins, phenolaralkyl resins (having a phenylene moiety),naphtholaralkyl resins, triphenolmethane resins, terpene-modified phenolresins and dicyclopentadiene-modified phenol resin, which may be usedalone or in combination of two or more. In the light of reliability inmoisture resistance as an epoxy resin composition for encapsulating asemiconductor chip, it is preferable that the resin contains Na or Clions as ionic impurities as little as possible.

An equivalence ratio of the number of epoxy groups in the total epoxyresin to the number of phenolic hydroxyl groups in the phenol resin,i.e., the epoxy number/the phenolic hydroxyl number, is preferably 0.7to 1.5 both inclusive. With the ratio within the range, an epoxy resinfor encapsulating a semiconductor chip exhibits excellent curingproperties. Furthermore, a cured product has an increasedglass-transition temperature and improved reliability in moistureresistance. When combining the epoxy resin (F) and the crystalline epoxyresin (A) with the phenol resin (B), the highest effects can be achievedin crack resistance and warpage, in soldering after moisture absorption.

Polybutadiene Having the Intramolecular Oxirane Structure (C-3)

A polybutadiene (C-3) used in this embodiment has the intramolecularoxirane structure. A content of the oxirane oxygen influencesadhesiveness. As determined in accordance with standard methods for theanalysis of fats, oils and related materials (oxirane oxygen), theoxirane-oxygen content is 3% to 10% both inclusive, more preferably 5%to 8% both inclusive. With the oxirane-oxygen content within the aboverange, adhesiveness of a cured product to a substrate is improved.Furthermore, fluidity of an epoxy resin composition can be improved,resulting in reliable filling.

A viscosity of the polybutadiene (C-3) having the intramolecular oxiranestructure influences viscosity of a resin composition for encapsulatinga semiconductor chip. A viscosity of an epoxy resin composition forencapsulating a semiconductor chip containing the polybutadiene (C-3) is20 Pa·s to 700 Pa·s both inclusive, more preferably 50 Pa·s to 500 Pa·sboth inclusive as determined at 25° C. in accordance with JIS Z-8803.With the viscosity within the above range, the epoxy resin compositionfor encapsulating a semiconductor chip exhibits improved fluidity.Furthermore, a cured product exhibits good adhesiveness to a substrateand warpage in a semiconductor device is minimized.

The polybutadiene (C-3) having an oxirane structure may be the compoundas represented by general formula (11). In this embodiment, thepolybutadiene (C-3) is essential.

The polybutadiene (C-3) can improve adhesiveness of an epoxy resincomposition with a metal substrate (for example, nickel-palladium ornickel-palladium-gold plating), resulting in high reflow heatresistance.

As long as effects of using the polybutadiene (C-3) are notdeteriorated, another stress-lowering agent may be combined. Examples ofa stress-lowering agent which can be combined, include silicone oilssuch as organopolysiloxanes and rubbers such as silicone rubbers andacrylonitrile rubbers which are solid at ambient temperature.

Its content is 0.05 wt % to 1.5 wt % both inclusive, preferably 0.1 wt %to 1 wt % both inclusive. With the content within the range, a curedproduct exhibits excellent adhesiveness to a substrate. Furthermore,fluidity of an epoxy resin composition can be improved, resulting inmore reliable filling.

Inorganic Filler (D)

An inorganic filler (D) used in Embodiment 3 may be the filler asdescribed in Embodiment 1. A content of the inorganic filler (D) is 85wt % to 95 wt % both inclusive, preferably 87 to 93 wt % both inclusivein the total epoxy resin composition. When the content of the inorganicfiller (D) is within the above range, a molding prepared may haveadequately reduced hygroscopicity and thermal expansion, resulting ingood soldering resistance and reduction in warpage in a semiconductordevice. Furthermore, fluidity of an epoxy resin composition forencapsulating a semiconductor chip can be improved, so that it can bereliably filled during molding and thus problems such as gold-wiredeformation can be prevented.

Curing Accelerator (E)

A curing accelerator (E) used in Embodiment 3 may be the compound asdescribed in Embodiment 1.

Epoxy Resin (F)

An epoxy resin (F) may be the epoxy resin represented by general formula(6).

As seen in formula (6), the epoxy resin (F) has hydrophobic and rigidbiphenylene moiety between epoxy groups. Thus, a cured product preparedfrom the epoxy resin composition containing the epoxy resin (F) hasreduced moisture-absorption rate and lower elasticity modulus in hightemperature range over glass-transition temperature (hereinafter,referred to as “Tg”). It also exhibits good adhesiveness to asemiconductor chip, an organic substrate and a metal substrate. It alsohas the feature that it exhibits higher heat resistance in spite of itslow crosslinking density.

The epoxy resin (F) may be, for example, a phenol biphenyl aralkyl typeepoxy resin, but there are no particular restrictions as long as it hasthe structure of general formula (6).

In general formula (6), when n is within the above range, an epoxy resincomposition exhibits improved curing properties and fluidity.

Silane Coupling Agent (G)

A silane coupling agent (G) used in Embodiment 3 may be a compoundrepresented by general formula (9). In this embodiment, the silanecoupling agent (G) is essential.

R3-NH—R4-Si (OR5)_(n)R6_(3-n)  (9)

wherein R3 is an organic group having 1 to 12 carbon atoms; R4, R5 andR6 are hydrocarbon having 1 to 12 carbon atoms and R3 to R6 are the sameor different; and n is integer of 1 to 3.

Using the silane coupling agent (G) represented by general formula (9),viscosity of an epoxy resin composition is lowered and thus its fluidityis improved. A content of the silane coupling agent (G) is, but notlimited to, 0.05 wt % to 1 wt % both inclusive, more preferably 0.1 wt %to 0.8 wt % both inclusive in the total epoxy resin composition. Withthe content of the silane coupling agent (G) within the range, a curedproduct exhibits good adhesiveness to a substrate. Furthermore, theepoxy resin composition is excellent in fluidity and curing properties.The silane coupling agent (G) represented by general formula (9) may beused alone or in combination of two or more.

As long as it does not deteriorate effects of using the silane couplingagent (G) represented by general formula (9), another coupling agent maybe combined. Examples of a coupling agent which can be combined, includesilane coupling agents such as epoxysilanes, mercaptosilanes,aminosilanes, alkylsilanes, ureidosilanes and vinylsilanes; titanatecoupling agents; aluminum coupling agents; and aluminum/zirconiumcoupling agents.

Other Components

The epoxy resin composition of Embodiment 3 may contain, in addition tocomponents (A) to (G), the additional components as described above.

The epoxy resin composition in Embodiment 3 can be prepared as describedin Embodiment 1. Furthermore, the epoxy resin composition can be used toencapsulate an electronic part such as a semiconductor chip to prepare asemiconductor device as described in Embodiment 1.

EMBODIMENT 4

An epoxy resin composition for encapsulating a semiconductor chip ofEmbodiment 4 contains the following components (A) to (F).

(A) a crystalline epoxy resin represented by general formula (4),

(B) a phenol resin represented by general formula (5),

(C-1) an epoxidized polybutadiene compound,

(D) an inorganic filler,

(E) a curing accelerator and

(F) an epoxy resin represented by general formula (6).

A weight ratio [(F)/(A)] of component (F) to component (A) is 10/90 to90/10 both inclusive. Component (D) is contained in the amount of 80 wt% to 94 wt % both inclusive in the total epoxy resin composition.Furthermore, the epoxidized polybutadiene compound (C-1) is contained inthe amount of 0.05 wt % to 5 wt % both inclusive in the total epoxyresin composition.

In general formula (4), X is group selected from single bond, —O—, —S—and —C(R2)₂—; R1s are alkyl having 1 to 6 carbon atoms and are the sameor different; m is integer of 0 to 4; R2s are hydrogen or alkyl having 1to 4 carbon atoms and are the same or different.

In general formula (5), R1 and R2 are hydrogen or alkyl having 1 to 4carbon atoms and are the same or different; a is integer of 0 to 3; b isinteger of 0 to 4; and n is average and is positive number of 1 to 5.

In general formula (6), R1 and R2 are hydrogen or alkyl having 1 to 4carbon atoms and are the same or different; a is integer of 0 to 3; b isinteger of 0 to 4; and n is average and is positive number of 1 to 5.

Such an epoxy resin composition can be used to provide a semiconductordevice with reduced warpage and excellent soldering crack resistance.The epoxy resin composition is, therefore, particularly suitable forencapsulating an area mounting type semiconductor.

There will be specifically described Embodiment 4.

Crystalline Epoxy Resin (A)

A crystalline epoxy resin (A) used in Embodiment 4 may be thecrystalline epoxy resin as described in Embodiment 3.

In Embodiment 4, the weight ratio [(F)/(A)] of the epoxy resin (F) tothe crystalline epoxy resin (A) is 10/90 to 90/10 both inclusive,preferably 20/80 to 70/30 both inclusive, particularly preferably 30/70to 50/50 both inclusive. When the weight ratio [(F)/(A)] is within therange, a cured product prepared from an epoxy resin composition exhibitslowered moisture absorbing rate. Furthermore, an inorganic filler can becontained in higher content in the epoxy resin composition. Thus, acured product can exhibit lower moisture absorbing rate and higherstrength.

In Embodiment 4, the additional epoxy resin as described in Embodiment 3can be added as long as it does not deteriorate the features obtained byusing the epoxy resin (F) and the crystalline epoxy resin (A). A contentof the additional epoxy resin is, if any, preferably such that the epoxyresin (F) and the crystalline epoxy resin (A) amount to 70 wt % to 100wt % both inclusive to the total epoxy resin. When the total amount ofthe epoxy resin (F) and the crystalline epoxy resin (A) is within therange, a cured product exhibits a reduced moisture-absorbing rate andfurther improved crack resistance.

Phenol Resin (B)

A phenol resin (B) used in Embodiment 4 may be the phenol resinrepresented by general formula (5) as described in Embodiment 3.

The above additional phenol resin may be combined as long as it does notdeteriorate the features obtained by using the phenol resin (B)represented by general formula (5) used in this embodiment. A content ofthe additional phenol resin combined is preferably such that the contentof the phenol resin (B) represented by general formula (5) is 70 wt % to100 wt % both inclusive in the total phenol resin. With the content ofthe phenol resin (B) within the above range, a cured product has reducedmoisture-absorption rate, and furthermore, exhibits excellentadhesiveness to a base material and soldering resistance aftersoldering.

An equivalence ratio of the number of epoxy groups in the total epoxyresin to the number of phenolic hydroxyl groups in the phenol resin,i.e., the epoxy number/the phenolic hydroxyl number, is preferably 0.7to 1.5 both inclusive. With the ratio within the range, a resincomponent exhibits excellent curing properties. Furthermore, a curedproduct has increased glass-transition temperature and improvedreliability in moisture resistance. When combining the epoxy resin (F)represented by general formula (6) and the crystalline epoxy resin (A)represented by general formula (4) with the phenol resin (B) representedby general formula (5), the highest effects can be achieved in crackresistance and warpage in soldering after moisture absorption.Epoxidized polybutadiene compound (C-1)

An epoxidized polybutadiene compound (C-1) used in this embodiment maybe the compound as described in Embodiment 1. Its content is preferably0.05 wt % to 5 wt % both inclusive, particularly preferably 0.1 wt % to2 wt % both inclusive to the total epoxy resin composition with thecontent within the range, an elastic modulus can be lowered andviscosity of the epoxy resin composition can be reduced.

The epoxidized polybutadiene compound (C-1) used in this embodimentpreferably has the number average molecular weight of 500 to 4000 bothinclusive. When the number average molecular weight is within the range,a cured product exhibits excellent soldering resistance, andfurthermore, increase in viscosity of the epoxy resin composition can beprevented.

Inorganic Filler (D)

An inorganic filler (D) used in Embodiment 4 may be the filler asdescribed in Embodiment 1. In the light of balance between moldabilityand reliability, the content of the total inorganic filler is preferably80 wt % to 94 wt % both inclusive in the total epoxy resin composition.A content within the range may lead to prevention of curing shrinkageduring molding/curing and thermal shrinkage from a molding temperatureto room temperature, resulting in reduced warpage. Furthermore,moisture-absorption rate of a cured product is lowered and thussoldering crack resistance is improved. In addition, fluidity isimproved, resulting in good moldability.

Curing Accelerator (E)

A curing accelerator (E) used in Embodiment 4 may be the compound asdescribed in Embodiment 1.

Epoxy Resin (F)

An epoxy resin (F) used in Embodiment 4 may be the epoxy resin asdescribed in Embodiment 3.

Other Components

An epoxy resin composition used in Embodiment 4 may contain, in additionto components (A) to (F), the additional components as described above.Furthermore, it may appropriately contain, if necessary, any of variousadditives including a coupling agent such asγ-glycidoxypropyltrimethoxysilane.

The epoxy resin composition used in this embodiment is prepared byblending components (A) to (F) and the other additives at ambienttemperature using a mixer, melt-kneading the mixture using kneadingmeans such as a roller mill, a kneader and an extruder, and cooling andthen milling the mixture.

The epoxy resin composition of Embodiment 4 can be prepared as describedin Embodiment 1. Furthermore, the epoxy resin composition can be used toencapsulate an electronic part such as a semiconductor chip to prepare asemiconductor device as described in Embodiment 1.

EMBODIMENT 5

An epoxy resin composition for encapsulating a semiconductor chip ofEmbodiment 5 contains the following components (A) to (C-2) and (F).

(A) a crystalline epoxy resin represented by general formula (4),

(B) a phenol resin represented by general formula (5),

(C-2) a butadiene-acrylonitrile copolymer and

(F) an epoxy resin represented by general formula (6).

In general formula (4), X is group selected from single bond, —O—, —S—and —C(R2)₂—; R1s are alkyl having 1 to 6 carbon atoms and are the sameor different; m is integer of 0 to 4; R2s are hydrogen or alkyl having 1to 4 carbon atoms and are the same or different.

In general formula (5), R1 and R2 are hydrogen or alkyl having 1 to 4carbon atoms and are the same or different; a is integer of 0 to 3; b isinteger of 0 to 4; and n is average and is positive number of 1 to 5.

In general formula (6), R1 and R2 are hydrogen or alkyl having 1 to 4carbon atoms and are the same or different; a is integer of 0 to 3; b isinteger of 0 to 4; and n is average and is positive number of 1 to 5.

Such an epoxy resin composition may meet both higher content of aninorganic filler and higher fluidity. Thus, it can provide a significanteffect that particularly an area mounting type semiconductor device canmeet both reduction in warpage and higher reliability such as improvedsoldering resistance.

There will be specifically described Embodiment 5.

Crystalline Epoxy Resin (A)

A crystalline epoxy resin (A) used in Embodiment 5 may be the epoxyresin represented by general formula (4) as described in Embodiment 3.

In Embodiment 5, the weight ratio [(F)/(A)] of an epoxy resin (F)described later to the crystalline epoxy resin (A) is preferably 10/90to 90/10 both inclusive, more preferably 20/80 to 70/30 both inclusive,particularly preferably 30/70 to 50/50 both inclusive. When the weightratio [(F)/(A)] is within the above range, a cured product from theepoxy resin composition can exhibit lower moisture-absorbing rate and aninorganic filler can be added in high content without deterioration influidity of the epoxy resin composition during molding, resulting inexcellent soldering resistance.

In Embodiment 5, the additional epoxy resin as described in Embodiment 3can be added as long as it does not deteriorate the features obtained byusing the epoxy resin (F) and the crystalline epoxy resin (A). A contentof the additional epoxy resin is, if any, preferably such that the epoxyresin (F) and the crystalline epoxy resin (A) amount to 70 wt % to 100wt % both inclusive to the total epoxy resin. When the total amount ofthe epoxy resin (F) and the crystalline epoxy resin (A) is within therange, a satisfactorily low moisture absorption and adequate solderingresistance can be achieved.

Phenol Resin (B)

A phenol resin (B) used in Embodiment 5 may be the phenol resinrepresented by general formula (5).

In this embodiment, as long as the effects obtained by using the phenolresin (B) are not deteriorated, the additional phenolic resin asdescribed in Embodiment 3 can be added. A content of the additionalphenolic resin combined is, if any, preferably such that the content ofthe phenol resin (B) is 40 wt % to 100 wt % both inclusive to the totalphenolic resin. When the content of the phenol resin (B) is within theabove range, a satisfactorily low moisture absorption and adequatesoldering resistance can be achieved.

Butadiene-Acrylonitrile Copolymer (C-2)

A butadiene-acrylonitrile copolymer (C-2) used in Embodiment 5 may be,but not limited to, the compound represented by general formula (3) asdescribed in Embodiment 2. A content of the butadiene-acrylonitrilecopolymer (C-2) is preferably 0.05 to 0.5 wt % both inclusive, morepreferably 0.1 to 0.3 wt % both inclusive in the total epoxy resincomposition. A content within the above range can lead to improvement inadhesiveness of a cured product to a base material. Furthermore,fluidity of the epoxy resin composition is improved, so that it can bereliably filled during molding. In addition, since the epoxy resincomposition becomes less viscous, for example, gold-wire deformationwithin a semiconductor device can be prevented.

Epoxy Resin (F)

An epoxy resin (F) used in Embodiment 5 may be the epoxy resinrepresented by general formula (6) as described in Embodiment 3.

An epoxy resin composition for encapsulating a semiconductor chip ofthis embodiment can contain, in addition to components (A) to (C-2) and(F) described above, an inorganic filler (D) and a curing accelerator(E).

Inorganic Filler (D)

An inorganic filler (D) used in Embodiment 5 may be the filler asdescribed in Embodiment 1. A content of the inorganic filler (D) ispreferably 80 wt % to 95 wt % both inclusive, more preferably 86 to 93wt % both inclusive in the total epoxy resin composition. The contentwithin the range may lead to prevention of soldering resistance frombeing deteriorated due to increase in moisture-absorbing rate andcoefficient of thermal expansion. In addition, warpage of a curedproduct can be prevented. Furthermore, fluidity of an epoxy resincomposition is improved and thus it can be reliably filled duringmolding. It allows for further lower viscosity, which can preventproblems such as gold-wire deformation within a semiconductor device.

Curing Accelerator (E)

A curing accelerator (E) used in Embodiment 5 may be the compound asdescribed in Embodiment 3.

An epoxy resin composition of this embodiment can contain, in additionto components (A) to (F), the additional components described above.Furthermore, it can appropriately contain, if necessary, any of variousadditives including a silane coupling agent such as epoxysilanes,mercaptosilanes, aminosilanes, alkylsilanes, ureidosilanes andvinylsilanes and coupling agents such as titanate coupling agents,aluminum coupling agents and aluminum/zirconium coupling agents.

The epoxy resin composition of Embodiment 5 can be prepared as describedin Embodiment 1. Furthermore, the epoxy resin composition can be used toencapsulate an electronic part such as a semiconductor chip to prepare asemiconductor device as described above.

EXAMPLES

This invention will be described with reference to, but not limited to,Examples. Here, any content shall be expressed as wt %.

Experimental Example A Experimental Example a-1

Epoxy resin 1: a biphenyl type epoxy resin (Japan Epoxy Resins Co.,Ltd., YX4000K, melting point: 105° C., epoxy equivalent: 185): 4.13 wt %

Phenol resin 1: a phenol aralkyl resin having a biphenylene moiety(Meiwa Plastic Industries, Ltd., MEH7851SS, softening point 65° C.,hydroxyl equivalent 203): 4.54 wt %

Triphenylphosphine: 0.13 wt %

Fused spherical silica (average particle size: 30 μm): 90.00 wt %

Epoxidized polybutadiene compound 1 (Nippon Petrochemicals Company,Limited, E-1800-6.5, number average molecular weight: 1800, viscosity(25° C.): 350 Pa·s): 0.50 wt %

γ-Glycidylpropyltrimethoxysilane: 0.20 wt %

Carnauba wax: 0.20 wt %

Carbon black: 0.30 wt %

These components were blended by a mixer. Then, the mixture was kneadedusing two rolls whose surface temperatures were 90° C. and 45° C. Aftercooling, the mixture was milled to give an epoxy resin composition. Theepoxy resin composition thus obtained was evaluated by the followingmethod. The results are shown in Table 1.

Evaluation Method

Spiral flow: determined mold temperature of 175° C., an injectionpressure of 6.9 MPa and curing time of 2 min, using a mold for measuringa spiral flow in accordance with EMMI-1-66. It is expressed in units ofcentimeter.

Package warpage: a 352-pin BGA was formed using a transfer moldingmachine under the conditions of mold temperature: 175° C., an injectionpressure: 6.9 MPa, curing time: 2 min, where a substrate was abismaleimide-triazine resin/glass fabric substrate with thickness of0.56 mm, a semiconductor device size was 30 mm×30 mm (thickness: 1.17mm), a semiconductor chip size was 10 mm×10 mm (thickness: 0.35 mm), anda semiconductor chip was bound with a bonding pad in a circuit board viaa gold wire with diameter of 25 μm. It was post-cured at 175° C. for 2hours to give a sample. A set of ten semiconductor devices thus preparedwas cooled to room temperature. Then, the displacement in heightdirection was measured in diagonal direction from the gate of thepackage, using a surface roughness gauge. The maximum displacementdifference was determined as warpage in units of micrometer (μm).

Gold-wire deformation rate: a 352-pin BGA package formed for evaluatinga package warpage was observed by a soft X-ray fluoroscope, to express agold-wire deformation rate as rate of (flow amount)/(gold-wire length)in units of %.

Soldering resistance: a 352-pin BGA package formed for evaluating apackage warpage was post-cured at 175° C. for 2 hours. A set of tenpackages thus prepared were treated under the atmosphere of temperatureof 60° C. and relative humidity of 60% for 168 hours, of temperature of85° C. and relative humidity of 60% for 168 hours, and then oftemperature of 85° C. and relative humidity of 85% for 72 hours. Then,the packages were subjected to IR reflow treatment at peak temperatureof 260° C. (at 255° C. or higher for 10 sec.). After treatment, thepresence of an internal detachment or crack was observed by anultrasonic flaw detector, and defective semiconductor devices werecounted. When the number of defective semiconductor devices was n, therate was expressed as n/10.

Experimental Examples a-2 to a-11 and b-1 to b-7

In accordance with the compositions described in Tables 1 and 2, epoxyresin compositions were prepared and evaluated as described inExperimental Example a-1. The evaluation results are shown in Tables 1and 2.

Components other than those used in Experimental Example a-1 are asfollows.

Epoxy resin 2: an ortho-cresol novolac type epoxy resin (epoxyequivalent: 196, softening point: 55° C.)

Phenol resin 2: a phenol aralkyl resin having a phenylene moiety (MitsuiChemicals Inc., XLC-LL, softening point: 75° C., hydroxyl equivalent:175)

Phenol resin 3: a phenol novolac resin (softening point: 80° C.,hydroxyl equivalent: 105)

1,8-Diazabicyclo(5,4,0)undecene-7 (hereinafter, referred to as “DBU”)

Epoxidized polybutadiene compound 2 (an number average molecular weight:700, viscosity (25° C.): 10 Pa·s)

Epoxidized polybutadiene compound 3 (an number average molecular weight:2000, viscosity (25° C.): 550 Pa·s)

TABLE 1 Experimental Example a-1 a-2 a-3 a-4 a-5 a-6 a-7 a-8 a-9 a-10a-11 Epoxy resin 1 4.13 3.20 5.07 4.31 3.64 2.10 4.31 4.95 4.13 4.134.13 Epoxy resin 2 2.10 Phenol resin 1 4.54 3.50 5.57 4.73 4.00 4.472.18 1.86 4.54 4.54 4.54 Phenol resin 2 2.18 Phenol resin 3 1.86Triphenylphosphine 0.13 0.10 0.16 0.16 0.16 0.13 0.13 0.13 0.13 0.13 DBU0.13 Fused spherical silica 90.00 92.00 88.00 90.00 90.00 90.00 90.0090.00 90.00 90.00 90.00 Epoxidized polybutadiene compound 1 0.50 0.500.50 0.10 1.50 0.50 0.50 0.50 0.50 Epoxidized polybutadiene compound 20.50 Epoxidized polybutadiene compound 3 0.50γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.200.20 0.20 0.20 Carnauba wax 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.200.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.300.30 Spiral flow (cm) 145 121 167 149 134 135 143 140 151 136 141Package warpage (μm) 38 14 54 36 42 38 36 35 37 39 39 Gold wiredeformation rate (%) 3 4 2 2 4 4 3 3 2 4 3 Soldering after treatment at60° C./60% for 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10resistance 168 hr after treatment at 85° C./60% for 0/10 0/10 2/10 1/100/10 2/10 1/10 2/10 1/10 0/10 0/10 168 hr after treatment at 85° C./85%for 2/10 0/10 4/10 3/10 0/10 5/10 3/10 5/10 2/10 1/10 2/10 72 hr

TABLE 2 Experimental Example b-1 b-2 b-3 b-4 b-5 b-6 b-7 Epoxy resin 14.37 1.51 1.31 7.42 4.46 5.53 Epoxy resin 2 4.26 Phenol resin 1 4.801.66 1.44 8.14 4.41 Phenol resin 2 4.21 Phenol resin 3 3.14Triphenylphosphine 0.13 0.13 0.05 0.24 0.13 0.13 0.13 Fused sphericalsilica 90.00 90.00 96.00 83.00 90.00 90.00 90.00 Epoxidizedpolybutadiene compound 1 6.00 0.50 0.50 0.50 0.50 0.50γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.20 0.20 0.20 0.20 0.20Carnauba wax 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.300.30 0.30 0.30 0.30 0.30 Spiral flow (cm) 150 87 35 230 64 149 156Package warpage (μm) 35 59 unfilled 112 40 37 36 Gold wire deformationrate (%) 2 8 unfilled 1 10 2 2 Soldering after treatment at 60° C./60%for 0/10 0/10 unfilled  7/10 0/10 1/10 2/10 resistance 168 hr aftertreatment at 85° C./60% for 4/10 0/10 unfilled 10/10 3/10 7/10 8/10 168hr after treatment at 85° C./85% for 6/10 0/10 unfilled 10/10 6/1010/10  10/10  72 hr

Experimental Example B Experimental Example a-1

Epoxy resin 1: a biphenyl type epoxy resin (Japan Epoxy Resins Co. Ltd.,YX4000K, melting point: 105° C., epoxy equivalent: 185): 4.29 wt parts

Phenol resin 1: a phenol aralkyl resin having a biphenylene moiety(Meiwa Plastic Industries, Ltd., MEH7851SS, softening point: 65° C.,hydroxyl equivalent: 203): 4.71 wt parts

Butadiene-acrylonitrile copolymer (Ube Industries, Ltd., HYCAR CTBN1008-SP, x=0.82, y=0.18, z=62 (average)): 0.15 wt parts

Triphenylphosphine: 0.15 wt parts

Fused spherical silica (average particle size: 30 μm): 90.00 wt parts

γ-Glycidylpropyltrimethoxysilane: 0.20 wt parts

Carnauba wax: 0.20 wt parts

Carbon black: 0.30 wt parts

These components were blended by a mixer. Then, the mixture was kneadedusing two rolls whose surface temperatures were 90° C. and 45° C. Aftercooling, the mixture was milled to give an epoxy resin composition. Theepoxy resin composition thus obtained was evaluated by the followingmethod. The results are shown in Table 3.

Evaluation Method

Spiral flow: measured under the conditions as described in ExperimentalExample A. A sample with a spiral flow of less than 100 cm was rejected.

Package warpage: measured under the conditions as described inExperimental Example A. A sample which was convex downward by 60 μm ormore was determined as defective.

Gold-wire deformation rate: determined under the conditions as describedin Experimental Example A. A sample with 3% or more was determined asdefective.

Soldering resistance: a 352-pin BGA package formed under the conditionsas described in terms of evaluating a package warpage was post-cured at175° C. for 2 hours. A set of ten packages thus prepared were treatedunder the atmosphere of temperature of 60° C. and relative humidity of60% for 168 hours or temperature of 85° C. and relative humidity of 60%for 168 hours. Then, the packages were subjected to IR reflow treatmentat peak temperature of 260° C. (at 255° C. or higher for 10 sec.). Aftertreatment, the presence of an internal detachment or crack was observedby an ultrasonic flaw detector and defective semiconductor devices werecounted. When the number of defective semiconductor devices was n, therate was expressed as n/10.

Experimental Examples a-2 to a-10 and b-1 to b-4

In accordance with the compositions described in Tables 3, 4 and 5,epoxy resin compositions were prepared and evaluated as described inExperimental Example a-1. The evaluation results are shown in Tables 3,4 and 5.

Components other than those used in Experimental Example a-1 were asfollows.

Epoxy resin 2: a triphenolmethane type epoxy resin (Japan Epoxy ResinsCo. Ltd., E-1032H60, softening point: 59° C., epoxy equivalent: 169)

Phenol resin 2: a phenol aralkyl resin having a phenylene moiety (MitsuiChemicals Inc., XLC-LL, softening point: 75° C., hydroxyl equivalent:175)

Phenol resin 3:a phenol novolac resin (softening point: 80° C., hydroxylequivalent: 105)

1,8-Diazabicyclo(5,4,0)undecene-7 (hereinafter, referred to as “DBU”)

γ-Mercaptopropyltrimethoxysilane

TABLE 3 Experimental Example a-1 a-2 a-3 a-4 a-5 Epoxy resin 1 4.29 3.305.16 4.40 4.95 Phenol resin 1 4.71 3.73 5.81 2.30 2.03 Phenol resin 22.30 Phenol resin 3 2.03 Butadiene-acrylonitrile copolymer 0.15 0.150.15 0.15 0.15 Triphenylphosphine 0.15 0.12 0.18 0.15 0.15 Fusedspherical silica 90.00 92.00 88.00 90.00 90.00γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.20 0.20 0.20 Carnauba wax0.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 Spiralflow (cm) 150 126 185 160 155 Package warpage (μm) 35 15 50 33 32 Goldwire deformation rate (%) 1.5 2.7 0.9 1.3 1.5 Soldering after treatmentat 60° C./60% for 0/10 0/10 0/10 0/10 0/10 resistance 168 hr aftertreatment at 85° C./60% for 0/10 0/10 0/10 0/10 0/10 168 hr

TABLE 4 Experimental Example a-6 a-7 a-8 a-9 a-10 Epoxy resin 1 3.404.25 4.16 4.29 4.29 Epoxy resin 2 0.85 Phenol resin 1 4.75 4.80 4.694.71 4.71 Butadiene-acrylonitrile copolymer 0.15 0.10 0.30 0.15 0.15Triphenylphosphine 0.15 0.15 0.15 0.15 DBU 0.15 Fused spherical silica90.00 90.00 90.00 90.00 90.00 γ-Glycidylpropyltrimethoxysilane 0.20 0.200.20 0.20 γ-Mercaptopropyltrimethoxysilane 0.20 Carnauba wax 0.20 0.200.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 Spiral flow (cm)121 160 130 155 125 Package warpage (μm) 12 37 25 35 26 Gold wiredeformation rate (%) 2.8 1.2 2.5 1.2 2.5 Soldering after treatment at60° C./60% for 0/10 0/10 0/10 0/10 0/10 resistance 168 hr aftertreatment at 85° C./60% for 0/10 0/10 0/10 0/10 0/10 168 hr

TABLE 5 Experimental Example b-1 b-2 b-3 b-4 Epoxy resin 1 4.59 5.764.31 Epoxy resin 2 4.09 Phenol resin 1 4.91 4.84 Phenol resin 2 4.41Phenol resin 3 3.24 Butadiene-acrylonitrile copolymer 0.15 0.15 0.15Triphenylphosphine 0.15 0.15 0.15 0.15 Fused spherical silica 90.0090.00 90.00 90.00 γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.20 0.20Carnauba wax 0.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 Spiralflow (cm) 155 154 82 95 Package warpage (μm) 31 32 5 37 Gold wiredeformation rate (%) 1.7 3.0 9.0 5.0 Soldering after treatment at 60°C./ 1/10 1/10 1/10  5/10 resistance 60% for 168 hr after treatment at85° C./ 5/10 7/10 3/10 10/10 60% for 168 hr

Experimental Example C Experimental Example a-1

Epoxy resin 1: a phenol biphenyl aralkyl type epoxy resin (Nippon KayakuCo. Ltd., NC3000P, epoxy equivalent: 274, softening point: 58° C.): 1.47wt parts

Epoxy resin 2: bisphenol-A type crystalline epoxy resin (Japan EpoxyResins Co. Ltd., YL6810, epoxy equivalent: 171, melting point: 45° C.):3.41 wt parts

Phenol resin 1: a phenol biphenyl aralkyl resin (Meiwa PlasticIndustries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening point:65° C.): 5.12 wt parts

Triphenylphosphine: 0.15 wt parts

Spherical fused silica (average particle size: 30 μm): 88.85 wt parts

Polybutadiene 1 (viscosity at 25° C.: 350 Pa·s, oxirane-oxygen content:6.5%): 0.30 wt parts

N-Phenyl γ-aminopropyltrimethoxysilane: 0.20 wt parts

Carnauba wax: 0.20 wt parts

Carbon black: 0.30 wt parts

These components were blended at ambient temperature by a mixer. Themixture was kneaded using two rolls at 70 to 120° C. After cooling, themixture was milled to give an epoxy resin composition. Epoxy resincompositions thus obtained were evaluated as described below. Theresults are shown in Table 6.

Evaluation Method

Spiral flow: measured under the conditions as described in ExperimentalExample A.

MAP molding (unfilled void): MAP-QFN (metal substrate: a copper frameplated with nickel-palladium-gold, encapsulating-area size: 45 mm×62 mm,thickness: 0.65 mm, size of a semiconductor device (QFN-16L) piece: 4.0mm×4.0 mm, semiconductor-element size: 1.5 mm×1.5 mm, thickness: 0.2 mm,passivation type: SiN) was molded under the conditions of moldtemperature: 175° C., an injection pressure: 6.9 MPa and curing time: 90sec using a transfer molding machine. Unfilled voids are counted.

Package warpage: for the MAP-QFN formed for evaluating MAP molding(unfilled void), the displacement in height direction was inlongitudinal direction using a surface roughness gauge. The maximumdisplacement difference was determined as package warpage in units ofmicrometer (μm).

Soldering crack resistance: the above MAP-QFN was formed and post-curedat 175° C. for 4 hours. It was then cut into individual pieces to obtainsemiconductor device (QFN-16L) samples. A set of twenty samples wasindividually treated under the conditions of temperature of 60° C. andrelative humidity of 60% for 120 hours and of temperature of 85° C. andrelative humidity of 60% for 168 hours. Then, the samples were treatedby IR reflow (260° C.) for 10 sec. Using an ultrasonic flaw detector,the samples were observed to determine the presence of various interfacedetachments. When the number of defective packages, in which detachmentoccurs, is n, the rate is expressed as n/20.

Experimental Examples a-2 to a-12 and b-1 to b-9

In accordance with the compositions described in Tables 6 and 7, epoxyresin compositions were prepared and evaluated as described inExperimental Example a-1. The evaluation results are shown in Tables 6and 7. Components other than those used in Experimental Example a-1 areas follows.

Epoxy resin 3: a biphenyl type epoxy resin (Japan Epoxy Resins Co. Ltd.,YX4000K, softening point: 105° C., epoxy equivalent: 185)

Phenol resin 2: a phenol aralkyl resin (Mitsui Chemicals Inc., XLC-LL,softening point: 75° C., hydroxyl equivalent: 175)

γ-Glycidylpropyltrimethoxysilane

Polybutadienes 2 to 6

An oxirane-oxygen content and viscosity at 25° C. for a polybutadieneare shown in Table 8.

TABLE 6 Experimental Example a-1 a-2 a-3 a-4 a-5 a-6 a-7 a-8 a-9 a-10a-11 a-12 Epoxy resin 1 1.47 2.55 0.50 4.97 2.53 2.01 1.47 1.47 1.331.47 1.38 1.47 Epoxy resin 2 3.41 2.55 4.18 0.62 2.53 2.98 3.41 3.413.07 3.41 3.21 3.41 Epoxy resin 3 0.55 Phenol resin 1 5.12 4.90 5.324.41 4.60 4.00 5.12 5.12 4.60 5.12 4.81 5.12 Phenol resin 2 1.01Triphenylphosphine 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 Spherical fused silica 88.85 88.85 88.85 88.85 88.85 88.8588.85 88.85 88.85 89.07 88.85 88.97 Polybutadiene 1 0.30 0.30 0.30 0.300.30 0.30 1.30 0.08 0.30 0.30 Polybutadiene 2 0.30 Polybutadiene 3 0.30Polybutadiene 4 Polybutadiene 5 Polybutadiene 6 N-Phenyl 0.20 0.20 0.200.20 0.20 0.20 0.20 0.20 0.20 0.20 0.80 0.08γ-aminopropyltrimethoxysilane γ-Glycidylpropyltrimethoxysilane Carnaubawax 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Carbonblack 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Spiralflow (cm) 110 100 140 92 113 110 123 95 93 101 95 100 MAP molding(number) 0 0 0 0 0 0 0 0 0 0 0 0 (unfilled void) MAP warpage (μm) 200180 300 150 250 220 200 210 160 200 220 200 Soldering (60° C./60%/120hr) 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/10resistance (85° C./60%/168 hr) 2/20 3/20 1/20 4/20 3/20 3/20 3/20 1/203/20 4/20 1/20 5/20

TABLE 7 Experimental Example b-1 b-2 b-3 b-4 b-5 b-6 b-7 b-8 b-9 Epoxyresin 1 5.75 2.00 2.36 0.47 1.47 1.47 1.47 1.47 Epoxy resin 2 4.59 2.905.46 1.00 3.41 3.41 3.41 3.41 Epoxy resin 3 Phenol resin 1 4.25 5.418.18 1.53 5.12 5.12 5.12 5.12 Phenol resin 2 5.10 Triphenylphosphine0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Spherical fused silica88.85 88.85 88.85 82.85 95.85 88.85 88.85 88.85 88.85 Polybutadiene 10.30 0.30 0.30 0.30 0.30 0.30 Polybutadiene 2 Polybutadiene 3Polybutadiene 4 0.30 Polybutadiene 5 0.30 Polybutadiene 6 0.30 N-Phenyl0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 γ-aminopropyltrimethoxysilaneγ-Glycidylpropyltrimethoxysilane 0.20 Carnauba wax 0.20 0.20 0.20 0.200.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.300.30 0.30 Spiral flow (cm) 78 155 100 110 30 78 130 60 110 MAP molding(number) 5 0 0 0 >20 8 0 20 0 (unfilled void) MAP warpage (μm) 140 350240 400 (*1) 200 250 200 200 Soldering (60° C./60%/120 hr) 0/20 0/200/20 0/20 (*1) 0/20 0/20 0/20  4/20 resistance (85° C./60%/168 hr) 2/202/20 8/20 2/20 (*1) 2/20 9/20 2/20 20/20 Note: *1; no evaluation sampleswere not obtained due to unfilling

TABLE 8 Polybutadiene 1 2 3 4 5 6 Oxirane-oxygen % 6.5 5 8 9 2 11 rateViscosity at 25° C. Pa-s 350 200 550 750 10 900

Experimental Example D Experimental Example a-1

Epoxy resin 1: a phenol biphenyl aralkyl type epoxy resin (Nippon KayakuCo. Ltd., NC3000P, epoxy equivalent: 274, softening point: 58° C.): 1.90wt parts

Epoxy resin 2: a bisphenol-A type crystalline epoxy resin (Japan EpoxyResins Co. Ltd., YL6810, epoxy equivalent: 171, melting point: 45° C.):2.85 wt parts

Phenol resin 1: a phenol biphenyl aralkyl resin (Meiwa PlasticIndustries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening point:65° C.): 4.65 wt parts

Triphenylphosphine: 0.20 wt parts

Spherical fused silica (average particle size: 30 μm): 89.00 wt parts

Epoxidized polybutadiene compound 1: Nippon Petrochemicals Co. Ltd.,E-1800-6.5, number average molecular weight: 1800, viscosity (25° C.):350 Pa·s: 0.50 wt parts

γ-Mercaptopropyltrimethoxysilane: 0.40 wt parts

Carnauba wax: 0.20 wt parts

Carbon black: 0.30 wt parts

These components were blended at ambient temperature by a mixer. Themixture was kneaded using two rolls at 70 to 120° C. After cooling, themixture was milled to give an epoxy resin composition. Epoxy resincompositions thus obtained were evaluated as described below. Theresults are shown in Table 9.

Evaluation Method

Spiral flow: measured under the conditions as described in ExperimentalExample A. When a spiral flow is less than 90 cm, fluidity is so lowthat defects such as unfilling may occur during molding a package.

Package warpage: a 352p BGA was formed using a transfer molding machineunder the conditions of mold temperature: 175° C., an injectionpressure: 6.9 MPa, curing time: 90 sec, where a substrate was abismaleimide-triazine resin/glass fabric substrate with thickness of0.56 mm, a semiconductor device size was 30 mm×30 mm (thickness: 1.17mm), a semiconductor chip size was 15 mm×15 mm (thickness: 0.35 mm). Itwas post-cured at 175° C. for 2 hours. After cooling to roomtemperature, the displacement in height direction was measured indiagonal direction from the gate of the package, using a surfaceroughness gauge. The maximum displacement difference was determined as apackage warpage in units of micrometer (μm) When a package warpage inthis package is 70 μm or more, the composition is not suitable as anencapsulator for encapsulating one side.

Gold-wire deformation rate: measured under the conditions as describedin Experimental Example A. When a gold-wire deformation rate is 4% ormore, short-circuit tends to occur due to contact between gold wires.

Soldering resistance: a 352pBGA was formed as described for evaluating apackage warpage and post-cured at 175° C. for 2 hours, to obtainsamples. A set of ten samples were individually wetted under theconditions of temperature of 60° C. and relative humidity of 60% for 168hours and of temperature of 85° C. and relative humidity of 60% for 168hours, and treated by IR reflow (260° C.) for 10 sec. The samples wereevaluated for the presence of inner cracks and various interfacedetachment by observing them by an ultrasonic flaw detector. When thenumber of defective packages is n, the rate is expressed as n/10. Whenthe number of defective packages is 3 or less, the sample passes thesoldering resistance evaluation test.

Experimental Examples a-2 to a-26

In accordance with the compositions described in Tables 9, 10 and 11,epoxy resin compositions were prepared and evaluated as described inExperimental Example a-1. The evaluation results are shown in Tables 9,10 and 11. Components other than those used in Experimental Example a-1are as follows.

Epoxy resin 3: an ortho-cresol novolac type epoxy resin (Nippon KayakuCo. Ltd., EOCN-1020-55, epoxy equivalent: 196, softening point: 55° C.)

Phenol resin 2: a phenol phenyl aralkyl resin (Mitsui Chemicals Inc.,XLC-LL, softening point: 75° C., hydroxyl equivalent: 175)

1,8-Diazabicyclo(5,4,0)undecene-7 (hereinafter, referred to as “DBU”).

Epoxidized polybutadiene compound 2: a compound represented by generalformula (4), wherein k, l, m and n are integer of 1 to 3; R1 hasstructure represented by C_(p)H_(q); p is integer of 0 to 3; and q isinteger of 1 to 8, number average molecular weight: 400, viscosity (25°C.): 150 Pas

Epoxidized polybutadiene compound 3: a compound represented by generalformula (4), wherein k, l, m and n are integer of 1 to 100; R1 hasstructure represented by C_(p)H_(q); p is integer of 0 to 10; and q isinteger of 1 to 21, number average molecular weight: 4500, viscosity(25° C.): 800 Pa·s

TABLE 9 Experimental Example a-1 a-2 a-3 a-4 a-5 a-6 a-7 a-8 a-9 Epoxyresin 1 1.90 0.91 3.56 5.47 1.42 1.13 1.93 1.94 Epoxy resin 2 2.85 3.644.37 1.53 2.13 1.70 2.90 2.91 Epoxy resin 3 1.18 1.89 Phenol resin 14.65 4.85 5.03 4.31 3.93 4.67 4.68 3.43 2.73 Phenol resin 2 1.14 1.82Triphenylphosphine 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 DBUSpherical fused silica 89.00 89.00 89.00 89.00 89.00 89.00 89.00 89.0089.00 Epoxidized polybutadiene compound 1 0.50 0.50 0.50 0.50 0.50 0.500.50 0.50 0.50 Epoxidized polybutadiene compound 2 Epoxidizedpolybutadiene compound 3 γ-Mercaptopropyltrimethoxysilane 0.40 0.40 0.400.40 0.40 0.40 0.40 0.40 0.40 γ-Glycldylpropyltrimethoxysilane Carnaubawax 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.300.30 0.30 0.30 0.30 0.30 0.30 0.30 Spiral flow (cm) 120 135 130 100 90130 115 130 125 Package warpage (μm) 50 67 79 43 53 57 64 56 57 Goldwire deformation rate (%) 2 1 2 3 5 2 3 2 2 Soldering after treatment at60° C./60% for 0/10 0/10 10/10 0/10 0/10 0/10 5/10 0/10 7/10 resistance168 hr after treatment at 85° C./60% for 0/10 0/10 10/10 0/10 0/10 1/106/10 1/10 9/10 168 hr

TABLE 10 Experimental Example a-10 a-11 a-12 a-13 a-14 a-15 a-16 a-17a-18 Epoxy resin 1 1.98 2.00 2.00 1.09 0.79 1.90 1.90 1.90 1.90 Epoxyresin 2 2.97 3.00 3.00 1.64 1.18 2.85 2.85 2.85 2.85 Epoxy resin 3Phenol resin 1 4.85 4.89 4.89 2.67 1.93 4.65 4.65 4.65 4.65 Phenol resin2 Triphenylphosphine 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 DBU 0.20Spherical fused silica 89.00 89.00 89.00 89.00 89.00 89.00 89.00 89.0089.00 Epoxidized polybutadiene compound 1 0.10 0.008 4.50 6.00 0.50 0.50Epoxidized polybutadiene compound 2 0.50 Epoxidized polybutadienecompound 3 0.50 γ-Mercaptopropyltrimethoxysilane 0.40 0.40 0.40 0.400.40 0.40 0.40 0.40 γ-Glycidylpropyltrimethoxysilane 0.40 Carnauba wax0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.300.30 0.30 0.30 0.30 0.30 0.30 Spiral flow (cm) 130 158 155 105 90 120 90115 115 Package warpage (μm) 44 50 50 64 79 72 100 53 53 Gold-linewiredeformation rate (%) 2 2 2 3 5 3 5 3 3 Soldering after treatment at 60°C./60% for 0/10 5/10 4/10 0/10 1/10 6/10 2/10 0/10 0/10 resistance 168hr after treatment at 85° C./60% for 2/10 6/10 5/10 1/10 2/10 8/10 3/100/10 0/10 168 hr

TABLE 11 Experimental Example a-19 a-20 a-21 a-22 a-23 a-24 a-25 a-26Epoxy resin 1 3.12 4.13 1.09 0.49 1.69 1.41 2.21 2.31 Epoxy resin 2 4.676.19 1.64 0.73 2.54 2.11 3.32 3.47 Epoxy resin 3 Phenol resin 1 7.6110.09 2.67 1.19 5.17 5.88 3.87 3.62 Phenol resin 2 Triphenylphosphine0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 DBU Spherical fused silica 83.0078.00 93.00 96.00 89.00 89.00 89.00 89.00 Epoxidized polybutadienecompound 1 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Epoxidizedpolybutadiene compound 2 Epoxidized polybutadiene compound 3γ-Mercaptopropyltrimethoxysilane 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40γ-Glycidylpropyltrimethoxysilane Carnauba wax 0.20 0.20 0.20 0.20 0.200.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30Spiral flow (cm) 140 >260 95 30 100 90 140 130 Package warpage (μm) 64114 41 unfilled 56 114 64 107 Gold wire deformation rate (%) 1 1 3unfilled 2 5 1 2 Soldering after treatment at 60° C./60% for 0/10 10/100/10 unfilled 0/10 10/10 0/10 10/10 resistance 168 hr after treatment at85° C./60% for 2/10 10/10 3/10 unfilled 3/10 10/10 2/10 10/10 168 hr

Experimental Example E Experimental Example a-1

Epoxy resin 1: a phenol biphenyl aralkyl type epoxy resin (Nippon KayakuCo. Ltd., NC3000, epoxy equivalent: 274, softening point: 58° C.): 2.55wt parts

Epoxy resin 2: a bisphenol-A type crystalline epoxy resin (Japan EpoxyResins Co. Ltd., YL6810, epoxy equivalent: 171, melting point: 45° C.):2.56 wt parts

Phenolic resin 1: a phenol biphenyl aralkyl resin (Meiwa PlasticIndustries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening point:65° C.): 4.89 wt parts

Butadiene-acrylonitrile copolymer 1 (Ube Industries, Ltd., HYCAR CTBN1008-SP; in general formula (3), x=0.82, y=0.18, z is 62 (the average)):0.15 wt parts

Triphenylphosphine: 0.15 wt parts

Fused spherical silica (average particle size: 30 μm): 89.00 wt parts

γ-Glycidylpropyltrimethoxysilane: 0.20 wt parts

Carnauba wax: 0.20 wt parts

Carbon black: 0.30 wt parts

These components were blended by a mixer. Then, the mixture was kneadedusing two rolls whose surface temperatures were 90° C. and 45° C. Aftercooling, the mixture was milled to give an epoxy resin composition. Theepoxy resin composition thus obtained was evaluated by the followingmethod. The results are shown in Table 12.

Evaluation Method

Spiral flow: measured under the conditions as described in ExperimentalExample A. A sample with a spiral flow of less than 90 cm was rejected.

Package warpage: measured under the conditions as described inExperimental Example A. A sample with warpage of 60 μm or more wasdetermined as defective.

Gold-wire deformation rate: determined under the conditions as describedin Experimental Example A. A sample with 3% or more was determined asdefective.

Soldering resistance: a 352-pin BGA package formed under the conditionsas described in terms of evaluating a package warpage was post-cured at175° C. for 2 hours. A set of ten packages thus prepared were treatedunder the atmosphere of temperature of 60° C. and relative humidity of60% for 168 hours or temperature of 85° C. and relative humidity of 60%for 168 hours. Then, the packages were subjected to IR reflow treatmentat peak temperature of 260° C. (at 255° C. or higher for 10 sec.). Aftertreatment, the presence of an internal detachment or crack was observedby an ultrasonic flaw detector, and defective semiconductor devices werecounted. When the number of defective semiconductor devices was n, therate was expressed as n/10.

Experimental Examples a-2 to a-22

In accordance with the compositions described in Tables 12, 13 and 14,epoxy resin compositions were prepared and evaluated as described inExperimental Example a-1. The evaluation results are shown in Tables 12,13 and 14.

Components other than those used in Experimental Example a-1 were asfollows.

Epoxy resin 3: a ortho-cresol novolac type epoxy resin (Nippon KayakuCo. Ltd., EOCN-1020-55, epoxy equivalent: 196, softening point: 55° C.)

Phenolic resin 2: a phenolic resin represented by general formula (12)(Tohto Kasei Co., Ltd., SN-485, softening point: 87° C., hydroxylequivalent: 210)

Phenolic resin 3: a phenol aralkyl resin having a phenylene moiety(Mitsui Chemicals Inc., XLC-LL, softening point: 75° C., hydroxylequivalent: 175)

Phenolic resin 4: a phenol novolac resin (softening point: 80° C.,hydroxyl equivalent: 105)

Butadiene-acrylonitrile copolymer 2 (Ube Industries, Ltd., HYCAR CTBN1300×13; in general formula (3), x=0.74, y=0.26, z=54 (the average))

1,8-Diazabicyclo(5,4,0)undecene-7 (hereinafter, referred to as “DBU”)

γ-Mercaptopropyltrimethoxysilane

TABLE 12 Experimental Example a-1 a-2 a-3 a-4 a-5 a-6 a-7 Epoxy resin 12.55 1.80 3.31 2.03 2.53 2.63 3.02 Epoxy resin 2 2.56 1.79 3.31 2.032.53 2.63 3.02 Epoxy resin 3 1.01 Phenol resin 1 4.89 3.44 6.35 4.932.47 3.32 1.98 Phenol resin 2 2.47 Phenol resin 3 1.42 Phenol resin 41.98 Butadiene-acrylonitrile copolymer 1 0.15 0.15 0.15 0.15 0.15 0.150.15 Triphenylphosphine 0.15 0.12 0.18 0.15 0.15 0.15 0.15 Sphericalfused silica 89.00 92.00 86.00 89.00 89.00 89.00 89.00γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.20 0.20 0.20 0.20 0.20Carnauba wax 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.300.30 0.30 0.30 0.30 0.30 Spiral flow (cm) 120 95 143 100 110 120 135Package warpage (μm) 40 27 55 50 40 50 44 Gold wire deformation rate (%)1.1 2.8 0.6 2.0 1.5 1.3 1.0 Soldering after treatment at 60° C./60% for0/10 0/10 0/10 0/10 0/10 0/10 0/10 resistance 168 hr after treatment at85° C./60% for 0/10 0/10 0/10 1/10 0/10 0/10 0/10 168 hr

TABLE 13 Experimental Example a-8 a-9 a-10 a-11 a-12 a-13 a-14 Epoxyresin 1 2.57 2.52 2.55 1.47 3.75 2.55 2.55 Epoxy resin 2 2.56 2.51 2.563.42 1.60 2.56 2.56 Epoxy resin 3 Phenol resin 1 4.92 4.82 4.89 5.114.65 4.89 4.89 Phenol resin 2 Phenol resin 3 Phenol resin 4Butadiene-acrylonitrile copolymer 1 0.10 0.30 0.15 0.15 0.15 0.15Butadiene-acrylonitrile copolymer 2 0.15 Triphenylphosphine 0.15 0.150.15 0.15 0.15 0.15 DBU 0.15 Spherical fused silica 89.00 89.00 89.0089.00 89.00 89.00 89.00 γ-Glycidylpropyltrimethoxysilane 0.20 0.20 0.200.20 0.20 0.20 γ-Mercaptopropylmethoxysilane 0.20 Carnauba wax 0.20 0.200.20 0.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.30Spiral flow (cm) 130 98 105 150 100 125 105 Package warpage (μm) 42 5048 52 38 45 40 Gold wire deformation rate (%) 0.90 2.2 1.9 0.5 2.0 1.11.9 Soldering after treatment at 60° C./60% for 0/10 0/10 0/10 0/10 0/100/10 0/10 resistance 168 hr after treatment at 85° C./60% for 0/10 0/100/10 1/10 0/10 0/10 0/10 168 hr

TABLE 14 Experimental Example a-15 a-16 a-17 a-18 a-19 a-20 a-21 a-22Epoxy resin 1 5.76 2.59 2.41 6.13 0.77 2.75 3.34 Epoxy resin 2 4.59 2.592.42 6.13 0.76 2.74 3.35 Phenol resin 1 5.41 4.24 4.97 4.62 11.74 1.47Phenol resin 3 4.51 Phenol resin 4 3.31 Butadiene-acrylonitrilecopolymer 1 0.15 0.15 0.70 0.15 0.15 0.15 0.15 Triphenylphosphine 0.150.15 0.15 0.15 0.15 0.15 0.15 0.15 Spherical fused silica 89.00 89.0089.00 89.00 75.00 96.00 89.00 89.00 γ-Glycidylpropyltrimethoxysilane0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Camauba wax 0.20 0.20 0.20 0.200.20 0.20 0.20 0.20 Carbon black 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30Spiral flow (cm) 165 77 124 85 160 54 125 135 Package warpage (μm) 58 3742 45 85 23 65 54 Gold wire deformation rate (%) 0.3 6.4 1.5 5.5 0.515.0 1.5 1.9 Soldering after treatment at 60° C./60% for  5/10 0/10 6/10 0/10 10/10 5/10 3/10  8/10 resistance 168 hr after treatment at85° C./60% for 10/10 0/10 10/10 0/10 10/10 8/10 6/10 10/10 168 hr

It is apparent that the present invention is not limited to the aboveembodiment, that may be modified and changed without departing from thescope and spirit of the invention.

1. An epoxy resin composition for encapsulating a semiconductor chipcomprising (A) a crystalline epoxy resin, (B) a phenol resin representedby general formula (1):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10, (C) a (co)polymercontaining butadiene-derived structural unit or its derivative, and (D)an inorganic filler in the amount of 80 wt % to 95 wt % both inclusivein the total epoxy resin composition.
 2. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 1, wherein saidphenol resin (B) is represented by general formula (2):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10; said (co)polymeror its derivative (C) is an epoxidized polybutadiene compound (C-1); andsaid inorganic filler (D) is contained in the amount of 85 wt % to 95 wt% both inclusive in the total epoxy resin composition.
 3. The epoxyresin composition for encapsulating a semiconductor chip as claimed inclaim 2, wherein the number average molecular weight of said epoxidizedpolybutadiene compound (C-1) is 500 to 4000 both inclusive.
 4. The epoxyresin composition for encapsulating a semiconductor chip as claimed inclaim 2, further comprising a curing accelerator (E).
 5. A semiconductordevice wherein a semiconductor chip is encapsulated with the epoxy resincomposition for encapsulating a semiconductor chip as claimed in claim2-4.
 6. The epoxy resin composition for encapsulating a semiconductorchip as claimed in claim 2-4 used for encapsulating an area mountingtype semiconductor device, wherein a semiconductor chip is mounted onone side of the substrate and substantially only the side of thesubstrate mounting the semiconductor chip is encapsulated.
 7. An areamounting type semiconductor device, wherein a semiconductor chip isencapsulated with the area mounting type epoxy resin composition forencapsulating a semiconductor chip as claimed in claim
 6. 8. The epoxyresin composition for encapsulating a semiconductor chip as claimed inclaim 1, wherein said phenol resin (B) is represented by general formula(2):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms and two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 4; b is integer of 0 to 4; c is integerof 0 to 3; and n is average and is number of 0 to 10, wherein said(co)polymer or its derivative (C) is a butadiene-acrylonitrile copolymer(C-2).
 9. The epoxy resin composition for encapsulating a semiconductorchip as claimed in claim 8, wherein said butadiene-acrylonitrilecopolymer (C-2) is a carboxyl-terminated butadiene-acrylonitrilecopolymer represented by general formula (3):

wherein Bu represents a butadiene-derived structural unit; ACNrepresents an acrylonitrile-derived structural unit; x is positivenumber of less than 1; y is positive number of less than 1; x+y=1; and zis integer of 50 to
 80. 10. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 8, wherein saidbutadiene-acrylonitrile copolymer (C-2) is contained in the amount of0.05 wt % to 0.5 wt % both inclusive in the total epoxy resincomposition.
 11. The epoxy resin composition for encapsulating asemiconductor chip as claimed in claim 8, wherein said inorganic filler(D) is contained in the amount of 85 wt % to 95 wt % both inclusive inthe total epoxy resin composition.
 12. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 8, furthercomprising a curing accelerator (E).
 13. A semiconductor device whereina semiconductor chip is encapsulated with the epoxy resin compositionfor encapsulating a semiconductor chip as claimed in claim 8-12.
 14. Theepoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 8-12 used for encapsulating an area mounting typesemiconductor device, wherein a semiconductor chip is mounted on oneside of the substrate and substantially only the side of the substratemounting the semiconductor chip is encapsulated.
 15. An area mountingtype semiconductor device, wherein a semiconductor chip is encapsulatedwith the area mounting type epoxy resin composition for encapsulating asemiconductor chip as claimed in claim
 14. 16. The epoxy resincomposition for encapsulating a semiconductor chip as claimed in claim1, wherein said crystalline epoxy resin (A) is represented by generalformula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different, said phenolresin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5, said (co)polymer or its derivative (C)is a polybutadiene having the intramolecular oxirane structure (C-3)with the oxirane-oxygen content of 3% to 10% both inclusive, and saidinorganic filler (D) is contained in the amount of 85 wt % to 95 wt %both inclusive in the total epoxy resin composition; and furthercomprising (F) an epoxy resin represented by general formula (6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to
 5. 17. The epoxy resincomposition for encapsulating a semiconductor chip as claimed in claim16, wherein said polybutadiene having the intramolecular oxiranestructure (C-3) has a viscosity of 20 Pa·s to 700 Pa·s both inclusive at25° C.
 18. The epoxy resin composition for encapsulating a semiconductorchip as claimed in claim 16, further comprising a curing accelerator(E).
 19. A semiconductor device wherein a semiconductor chip isencapsulated with the epoxy resin composition for encapsulating asemiconductor chip as claimed in claim 16-18.
 20. The epoxy resincomposition for encapsulating a semiconductor chip as claimed in claim16-18 used for encapsulating an area mounting type semiconductor device,wherein a semiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.
 21. An area mounting type semiconductor device,wherein a semiconductor chip is encapsulated with the area mounting typeepoxy resin composition for encapsulating a semiconductor chip asclaimed in claim
 20. 22. The epoxy resin composition for encapsulating asemiconductor chip as claimed in claim 1, wherein said crystalline epoxyresin (A) is represented by general formula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different, said phenolresin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5, and said (co)polymer or its derivative(C) is an epoxidized polybutadiene compound (C-1), said inorganic filler(D) is contained in the amount of 80 wt % to 94 wt % both inclusive inthe total epoxy resin composition; further comprising (F) an epoxy resinrepresented by general formula (6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to 5; and wherein the weight ratio[(F)/(A)] of said epoxy resin (F) to said crystalline epoxy resin (A)represented by general formula (4) is 10/90 to 90/10 both inclusive. 23.The epoxy resin composition for encapsulating a semiconductor chip asclaimed in 22, wherein said epoxidized polybutadiene compound (C-1) hasthe number average molecular weight of 500 to 4000 both inclusive. 24.The epoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 22, further comprising a curing accelerator (E).
 25. Asemiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 22-24.
 26. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 22-24 used forencapsulating an area mounting type semiconductor device, wherein asemiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.
 27. An area mounting type semiconductor device,wherein a semiconductor chip is encapsulated with the area mounting typeepoxy resin composition for encapsulating a semiconductor chip asclaimed in claim
 26. 28. The epoxy resin composition for encapsulating asemiconductor chip as claimed in claim 1, wherein said crystalline epoxyresin (A) is represented by general formula (4):

wherein X is group selected from single bond, —O—, —S— and —C(R2)₂—; R1is alkyl having 1 to 6 carbon atoms; two or more R1s are the same ordifferent; m is integer of 0 to 4; R2 is hydrogen or alkyl having 1 to 4carbon atoms; and two or more R2s is the same or different, said phenolresin (B) is represented by general formula (5):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3; b is integer of 0 to 4; n is averageand is positive number of 1 to 5, and said (co)polymer or its derivative(C) is a butadiene-acrylonitrile copolymer (C-2); and further comprising(F) an epoxy resin represented by general formula (6):

wherein R1 and R2 are independently hydrogen or alkyl having 1 to 4carbon atoms; two or more R1s or two or more R2s are the same ordifferent; a is integer of 0 to 3, b is integer of 0 to 4; and n isaverage and is positive number of 1 to
 5. 29. The epoxy resincomposition for encapsulating a semiconductor chip as claimed in claim28, wherein said butadiene-acrylonitrile copolymer (C-2) is acarboxyl-terminated butadiene-acrylonitrile copolymer represented bygeneral formula (3):

wherein Bu represents a butadiene-derived structural unit; ACNrepresents an acrylonitrile-derived structural unit; x is positivenumber of less than 1; y is positive number of less than 1; x+y=1; and zis integer of 50 to
 80. 30. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 28, wherein saidbutadiene-acrylonitrile copolymer (C-2) is contained in the amount of0.05 wt % to 0.5 wt % both inclusive in the total epoxy resincomposition.
 31. The epoxy resin composition for encapsulating asemiconductor chip as claimed in claim 28, wherein the weight ratio[(F)/(A)] of the epoxy resin (F) to the crystalline epoxy resin (A)represented by general formula (4) is 10/90 to 90/10 both inclusive. 32.The epoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 28, further comprising a curing accelerator (E).
 33. Asemiconductor device wherein a semiconductor chip is encapsulated withthe epoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 28-32.
 34. The epoxy resin composition forencapsulating a semiconductor chip as claimed in claim 28-32 used forencapsulating an area mounting type semiconductor device, wherein asemiconductor chip is mounted on one side of the substrate andsubstantially only the side of the substrate mounting the semiconductorchip is encapsulated.
 35. An area mounting type semiconductor device,wherein a semiconductor chip is encapsulated with the area mounting typeepoxy resin composition for encapsulating a semiconductor chip asclaimed in claim 34.